2-(4-pyrazolyloxy-pyrimidin-5-yl) acetic acid derivatives

ABSTRACT

This invention relates to novel 2-(4-pyrazolyloxy-pyrimidin-5-yl) acetic acid derivatives of formula I    &lt;IMAGE&gt;  (I)  wherein R1 is hydrogen, C1-4alkyl, C1-4alkoxy, C1-4alkylthio, C3-6cycloalkyl, or di-C1-4alkylamino, R2 is hydrogen, C1-4alkyl, C1-4alkoxy, C1-4alkylthio, or di-C1-4alkyl-amino, R3 is hydrogen or methyl, R4 is aryl, aryl-C1-4alkyl, heteroaryl, or heteroaryl-C1-4alkyl, wherein each of the aromatic rings may be optionally substituted; and X is CH or nitrogen; the use of such compounds for the control of phytopathogens, compositions for facilitating such use, and the preparation of the compounds of formula I.

This invention relates to novel 2-(4-pyrazolyloxy-pyrimidin-5-yl) aceticacid derivatives, the synthesis thereof and the use of said compoundsfor the control of phytopathogens.

It has now been found that compounds of formula I ##STR2## wherein R₁ ishydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ alkylthio, C₃₋₆ cycloalkyl, ordi-C₁₋₄ alkylamino,

R₂ is hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ alkylthio, or di-C₁₋₄alkyl-amino,

R₃ is hydrogen or methyl,

R₄ is aryl, aryl-C₁₋₄ alkyl, heteroaryl, or heteroaryl-C₁₋₄ alkyl ,wherein each of the aromatic rings may be optionally substituted; and

X is CH or nitrogen;

are surprisingly effective against phytopathogens.

In the definitions of the radicals of formula I alkyl is understood toencompass straight-chain and branched alkyl groups. For example alkyl ismethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl orsecondary butyl. Alkoxy for example encompasses methoxy, ethoxy,n-propoxy, isopropoxy, n-butyloxy, isobutyloxy, tertiary butyloxy orsecondary butyloxy. Alkylthio designates methylthio, ethylthio,isopropylthio, propylthio, n-butylthio, isobutylthio, tertiary butylthioor secondary butylthio. Cycloalkyl designates for example cyclopropyl,cyclobutyl, cyclopentyl or cyclohexyl. Dialkylamino designated forexample dimethylamino, diethylamino, dipropylamino, ethylmethylamino,ethylpropylamino, methylbutylamino, methylpropylamino, orethylbutylamino. Aryl stands for aromatic hydrocarbon radicals, forexample phenyl or naphthyl, with phenyl being preferred. The arylradical may optionally be further substituted. Heteroaryl stands foraromatic 5- or 5-membered cyclic radicals comprising one, two or threering atoms selected from nitrogen, oxygen and sulfur, which may also bein condensed form with another heteroaryl radical or aryl radical.Heteroaryl is linked to the oxygen bridge through a ring member carbonatom. The heteroaryl may optionally be further substituted. Examples forheteroaryl are pyridyl, pyrimidinyl, thienyl, oxazolyl, oxadiazolyl,triazolyl, thiadiazolyl, furyl, isoxazolyl, thiazolyl, imidazolyl,pyridazinyl, quinolinyl, quinazolinyl, benzothienyl, benzofuryl,benzimidazolyl, pyrazolyl, benzothiazolyl, benzoxazolyl, and the like.Arylalkyl preferably designates phenylalkyl such as benzyl, phenylethyl,phenylpropyl, or 1-phenylethyl. The aryl radical may optionally befurther substituted. Heteroarylalkyl designates an aromatic 5- or6-membered cyclic radical comprising one, two or three ring atomsselected from nitrogen, oxygen and sulfur, being linked to the oxygenbridge through an alkylene group, like --CH₂ --, --CH₂ --CH₂ -- or--CH(CH₃)--. The heteroaryl radical is linked to the alkylene groupthrough a ring member carbon atom. Examples for heteroarylalkyl arethienylmethyl, thienylethyl, furylmethyl, pyridylmethyl, pyrrolylmethyland the like. The pyrazolyl ring may be linked to the oxygen bridge viathe 3- or 4-position. However, 3-pyrazolyl is preferred.

In radicals being combined from various other definitions, each of thedefinitions has the meanings given for the partial definitionseparately.

The above aryl and heteroaryl radicals may be further substituted. Wherearyl or heteroaryl is substituted, it is preferably substituted by one,two or three radicals selected from the group comprising halogen, C₁₋₄alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, C₂₋₈ acyl, benzoyl,C₁₋₄ alkylthio, cyano, phenyl, phenoxy, nitro, or a group--C(CH₃)═N--O--C₁₋₄ alkyl. Halogen designates fluorine, chlorine,bromine and iodine, with fluorine and chlorine being preferred.Haloalkyl designates straight chain or branched alkyl groups which aremono- to perhalogenated with straight-chain lower alkyl being thepreferred alkyl and with fluorine perhalogenated with straight-chainlower alkyl being the preferred alkyl and with fluorine and chlorinebeing preferred halogens. Examples are trifluoromethyl, difluoromethyl,2,2,2-trifluoroethyl or 2,2,3,3,3-pentafluoropropyl. Haloalkoxydesignates alkoxy groups which are mono- to perhalogenated. Examples aredifluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy or1,1,2,2-tetrafluoroethoxy. Examples for acyl are acetyl, propionyl,butyroyl, isopropionyl, hexanoyl or octanoyl.

Preferred subgroups of compounds of formula I or those wherein either

a) R₁ is methyl, ethyl, or cyclopropyl; or

b) R₂ is methyl or methoxy; or

c) the pyrazole ring is linked to the oxygen bridge in 3- or 4-position;or

d) R₄ is chlorophenyl, dichlorophenyl, fluorophenyl,methyl-chlorophenyl, trifluoromethylphenyl,trifluoromethyl-chlorophenyl, difluoromethoxyphenyl,trifluoromethoxyphenyl, methylphenyl, or dimethylphenyl.

A further preferred subgroup is wherein R₁ and R₂ are methyl, and R₄ ischlorophenyl, dichlorophenyl, fluorophenyl, methyl-chlorophenyl,trifluoromethylphenyl, trifluoromethyl-chlorophenyl,difluoromethoxyphenyl, trifluoromethoxyphenyl, methylphenyl, ordimethylphenyl.

Among this subgroup those compounds are preferred wherein X is CH.

Preferred individual compounds of formula I are:

methyl 2-2,4-dimethyl-6-(1-(3-trifluoromethylphenyl)-1H)-pyrazol-3-yloxy)-pyrimidin-5-yl!-3-methoxyacrylate;

methyl 2-2,4-dimethyl-6-(1-(3,5-dimethylphenyl)-1H-pyrazol-4-yloxy)-pyrimidin-5-yl!-3-methoxyacrylate;

methyl 2-2,4-dimethyl-6-(1-(5-chloro-2-methylphenyl)-1H-pyrazol-3-yloxy)-pyrimidin-5yl!-3-methoxyacrylate;and

methyl 2-2-methyl-4-methoxy-6-(1-(5-chloro-2-methylphenyl)-1H-pyrazol-3-yloxy)-pyrimidin-5-yl!-3-methoxyacrylate.

The double bond of the acrylic acid structure in the compounds offormula I may be in E- or Z-form. In this document the E- and Z-formsare identified where meant specifically. In all other cases mixtures ofthe two isomers are intended. Where E- and Z-isomers are obtained duringsynthesis they may be separated by known techniques, such ascrystallisation, chromatography or distillation. In the describedmethods of preparation preferably the E-forms are obtained.

Compounds of formula I may be obtained by O-methylation of a compound offormula II ##STR3## wherein R₁, R₂, R₃, R₄ and X are as defined above.

The O-methylation (II→I) can be carried out in a manner known per se forthe preparation of 3-methoxyacrylates employing conventional methylationagents. Examples of suitable methylation agents include methyl iodideand dimethyl sulphate. The O-methylation is conveniently carried out inthe presence of a base. The reaction temperature will conveniently liein the range of from 0° C. to the boiling point of the reaction mixture,e.g. at about ambient temperature. Inert solvents may be used wheredesired. Examples of suitable bases include alkaline metal hydrides suchas sodium hydride, alkaline metal alcoholates such as sodium methylateor alkaline metal carbonates. Examples of suitable inert solventsinclude aromatic hydrocarbons such as benzene and toluene; ethers suchas diethyl ether, tetrahydrofuran and 1,2-dimethoxyethane; polarsolvents such as dimethylformamide, dimethyl sulfoxide, alcohols such asmethanol; acetone or a mixture comprising two or more of them. Thedesired end-product is isolated and purified according to knowntechniques, for example by evaporation of solvent, chromatography andcrystallisation.

The compounds of formula I are only slightly basic in nature. They mayform salts with sufficiently strong acids such as HCl and HBr.

The compounds of formula II wherein X is CH may be obtained by reactionof compounds of formula III ##STR4## wherein R₁, R₂, R₃ and R₄ are asdefined above and alkyl is C₁₋₁₀ alkyl, with a formylating agent, e.g.N,N-diformylmethylamine, or methyl formate in the presence of a base.

This reaction is essentially a Claisen reaction and may be carried outunder the conditions known for such reaction. The reaction (III→II) maybe carried out in an inert solvent. Examples of suitable solvents are asdescribed for the O-methylation of the compounds of formula II. Examplesof suitable bases are such typically used for a Claisen reaction such asalkaline metal alcoholates, e.g. sodium methylate; alkaline metalhydrides, e.g. sodium hydride; and lithium amides or sodium amides, e.g.lithium diethylamide. The reaction temperature may vary within wideranges, e.g. from 0° C. to the boiling point of the reaction mixture andis preferably at or near ambient temperature.

In an alternative process the compounds of formula II may also beobtained by reacting the compounds of formula III with a 1:1-adduct ofdimethylformamide and dimethylsulfate in the presence of a strong base,such as t-BuOK and hydrolysing the obtained intermediate of formula IIIa##STR5## wherein R₁, R₂ and R₃ are as defined above.

This reaction variant is preferably carried out in an inert solvent attemperature between -70° C. to -30° C., preferably -60° C. to -40° C.Suitable solvents are ethers like tetrahydrofuran, dioxane, diethyletheror glyme. Suitable bases are e.g. alkaline alcolates like t-BuOK; oralkaline hydrides like NaH, KH. The hydrolysing step is typically donein a two-phase system, by adding water, and at a temperature of 0° C. to+40° C., preferably at room temperature.

The compound of formula II wherein X is nitrogen may be obtained byreaction of compounds of formula III with an alkyl nitrite in thepresence of a base, optionally in the presence of an inert solvent. In avariant of this process the compounds of formula II wherein X is N mayalso be obtained by reacting a compound of formula III with an alkylnitrite in the presence of hydrochloric acid, optionally in an inertsolvent. The reaction temperature will conveniently lie in the range offrom -40° C. to +30° C. e.g. at about -20° C. to 0° C. Inert solventsmay be used where desired. Examples of suitable bases include alkalinemetal hydrides such as sodium hydride and alkaline metal alcoholatessuch as potassium tert.-butylate. Examples of suitable inert solventsinclude aromatic hydrocarbons such as benzene and toluene; ethers suchas diethyl ether, tetrahydrofuran and 1,2-dimethoxyethane; polarsolvents such as dimethylformamide, dimethyl sulfoxide, alcohols such astert.-butanol; or a mixture comprising two or more of them.

In a variant of the two-step process (III→II→I), the compounds offormula I may be obtained by a single-vessel reaction from compounds offormula III, without isolation and purification of the intermediatecompounds of formula II.

The acetic acid esters of formula III may be obtained from compounds offormula IV ##STR6## wherein R₁ and R₂ are as defined above, by reactingit with a hydroxy-pyrazole of formulae V or VI ##STR7## wherein R₃ andR₄ are as defined above in the presence of a base and an inert solvent.Suitable bases and solvents are as for (II→I).

The compounds of formula IV wherein R₂ is hydrogen, alkyl, alkoxy, ordialkylamino are known from EP-A-634 495 and EP-A-667 343.

The compounds of formula IV wherein R₂ is alkylthio may be obtained byreacting a compound of formula VII ##STR8## wherein R₁ is as definedabove with a mercaptane of formula VIII

    H--S--R.sub.2                                              (VIII)

wherein R₂ is as defined above, in the presence of a base.

This reaction is preferably carried out in an inert solvent such as anether, e.g. glyme (dimethoxyethane). Suitable bases are sodium hydride,sodium methylate or the like. In a preferred variant the base is reactedwith the mercaptane first to give the sodium salt, which may then bereacted with the compound of formula VII without the presence of a base.

Alternatively the intermediates of formula III wherein R₂ is C₁₋₄ alkoxyor di-C₁₋₄ alkylamino may be obtained by reacting the starting materialdichloropyrimidinyl acetic esters of formula VII with a hydroxypyrazoleof formulae V or VI first, and reacting the obtained intermediates offormula IX ##STR9## wherein R₁, R₃ and R₄ are as defined above, with acompound of formula X

    H--R.sub.2                                                 (X)

wherein R₂ is C₁₋₄ alkyloxy or di-C₁₋₄ alkylamino, in the presence of abase.

The reaction conditions for this synthesis variant (VII+V/VI→IX+X→III)are similar to those given for the reaction of VII with VIII.

The intermediates of formulae II, III and IX have especially beendeveloped for the synthesis of compounds of formula I. They thereforeconstitute a part of present invention.

The starting materials of formulae, IV, V, VI, VII and VIII are known,or may be prepared in analogy to known processes.

The compounds of formula V wherein R₄ is aryl or heteroaryl, eachoptionally substituted, may preferably be obtained by using a newoxidation procedure which has been especially developed for thesynthesis of the compounds of formula I. It is therefore part of thepresent invention.

The new oxidation procedure for preparing the compounds of formula V,wherein R₄ is aryl or heteroaryl, each optionally substituted comprisesoxidising the parent aryl- or heteroarylpyrazolidone of formula XI##STR10## wherein R₄ is aryl or heteroaryl, each optionally substituted,with an oxidising agent, prepared in situ from H₂ O₂ and a catalyst.

The oxidation step (XI→V) is preferably carried out in an inert solvent,like formic acid or acetic acid, at low temperatures. Preferably, theexothermic oxidation process is controlled by cooling, or by controlledaddition of the oxidising agent. Temperatures are preferably kept below+50° C., especially in the range of 0° C. to +30° C. Suitable oxidisingagents are H₂ O₂ in the presence of oxidation catalysts. Suitableoxidation catalysts are vanadyl acetylacetonate, copper (II)acetylacetonate, manganese oxide (MnO₂), selenium oxide (SeO₂), nickeloxide (NiO₂), and the like.

The compounds of formula I are effective against phytopathogens,including phytopathogenic fungi.

Their advantageous fungicidal activity is established by in vivo testswith test concentrations from 0.1 to 500 mg a.i./l against Uromycesappendiculatus on pole beans, against Puccinia triticina on wheat,against Sphaerotheca fuliginea on cucumber, against Erysiphe graminis onwheat and barley, against Podosphaera leucotricha on apple, againstUncinula necator on grape vine, against Leptosphaeria nodorum on wheat,against Cochliobolus sativus and Pyrenophora graminea on barley, againstVenturia inaequalis on apple, against Phytophthora infestans on tomatoand against Plasmopara viticola on grape vine.

Many of the compounds of formula I have an excellent plant tolerance anda systemic action. The compounds of the invention are thereforeindicated for treatment of plant, seeds and soil to combatphytopathogenic fungi, e.g. Basidiomycetes of the order Uredinales(rusts) such as Puccinia spp, Hemileia spp, Uromyces spp; andAscomycetes of the order Erysiphales (powdery mildew) such as Erysiphessp, Podosphaera spp, Uncinula spp, Sphaerotheca spp; as well asCochliobolus; Pyrenophora spp; Venturia spp; Mycosphaerella spp;Leptosphaeria; Deuteromycetes such as Pyricularia, Pellicularia(Corticium), Botrytis; and Oomycetes such as Phytophthora spp,Plasmopara spp.

The compounds of formula I are particularly effective against powderymildew and rust, pyrenophora and leptosphaeria fungi, in particularagainst pathogens of monocotyledoneous plants such as cereals, includingwheat and barley.

The amount of compound of the invention to be applied, will depend onvarious factors such as the compound employed, the subject of thetreatment (plant, soil, seed), the type of treatment (e.g. spraying,dusting, seed dressing), the purpose of the treatment (prophylactic ortherapeutic), the type of fungi to be treated and the application time.

In general, satisfactory results are obtained, if the compounds of theinvention are applied in an amount of from about 0.01 to 2.0, preferablyabout 0.02 to 1 kg/ha, in the case of a plant or soil treatment; e.g.0.04 to 0.500 kg of active ingredient (a.i.) per ha in field crops suchas cereals, or concentrations of 4 to 50 g of a.i. per hl in crops suchas fruits, vineyards and vegetables (at an application volume of from300 to 1000 l/ha--depending on the size or leaf volume of thecrop--which is equivalent to an application rate of approximately 30-500g/ha). The treatment can, if desired, be repeated, e.g. at intervals of8 to 30 days.

Where the compounds of the invention are used for seed treatment,satisfactory results are in general obtained, if the compounds are usedin an amount of from about 0.05 to 0.5, preferably about 0.1 to 0.3 g/kgseeds.

The term soil as used herein is intended to embrace any conventionalgrowing medium, whether natural or artificial.

The compounds of the invention may be used in a great number of crops,such as soybean, coffee, ornamentals (i.a. pelargonium, roses),vegetables (e.g. peas, cucumber, celery, tomato and bean plants),sugarbeet, sugarcane, cotton, flax, maize (corn), vineyards, pomes andstone fruits (e.g. apple, pears, prunes) and in cereals (e.g. wheat,oats, barley, rice).

The invention also provides fungicidal compositions, comprising as afungicide a compound of formula I in association with a agriculturallyacceptable diluent (hereinafter diluent). They are obtained inconventional manner, e.g. by mixing a compound of the invention with adiluent and optionally additional ingredients, such as surfactants. Theterm diluents as used herein means liquid or solid agriculturallyacceptable material, which may be added to the active agent to bring itin an easier or better applicable form, resp. to dilute the active agentto a usable or desirable strength of activity. Examples of such diluentsare talc, kaolin, diatomaceous earth, xylene or water.

Especially formulations used in spray form such as water dispersibleconcentrates or wettable powders, may contain surfactants such aswetting and dispersing agents, e.g. the condensation product offormaldehyde with naphthalene sulphonate, an alkylarylsulphonate, alignin sulphonate, a fatty alkyl sulphate, an ethoxylated alkylphenoland an ethoxylated fatty alcohol.

In general, the formulations include from 0.01 to 90% by weight ofactive agent, from 0 to 20% agriculturally acceptable surfactant andfrom 10 to 99.99% diluent(s). Concentrated forms of composition, e.g.emulsion concentrates, contain in general from about 2 to 90%,preferably from between 5 and 70% by weight of active agent. Applicationforms of formulation contain in general from 0.0005 to 10% by weight ofa compound of the invention as active agent typical spray-suspensionsmay, for example, contain from 0.0005 to 0.05, e.g. 0.0001, 0.002 or0.005% by weight of active agent.

In addition to the usual diluents and surfactants, the compositions ofthe invention may comprise further additives with special purposes, e.g.stabilisers, desactivators (for solid formulations or carriers with anactive surface), agents for improving the adhesion to plants, corrosioninhibitors, anti-foaming agents and colorants. Moreover, furtherfungicides with similar or complementary fungicidal activity, e.g.sulphur, chlorothalonil, euparen; a guanidine fungicide such asguazatine; dithiocarbamates such as mancozeb, maneb, zineb, propineb;trichloromethane sulphenylphthalimides and analogues such as captan,captafol and folpet; benzimidazoles such as carbendazim, benomyl; azolessuch as cyproconazole, flusilazole, flutriafol, hexaconazole,propiconazole, tebuconazole, epoxiconazole, triticonazole, prochloraz;morpholines such as fenpropimorph, fenpropidine, or otherbeneficially-acting materials, such as cymoxanil, oxadixyl, metalaxyl,or insecticides may be present in the formulations.

Examples of plant fungicide formulations are as follows:

a. Wettable Powder Formulation

10 Parts of a compound of formula I are mixed and milled with 4 parts ofsynthetic fine silica, 3 parts of sodium lauryl sulphate, 7 parts ofsodium lignin sulphonate and 66 parts of finely divided kaolin and 10parts of diatomaceous earth until the mean particle size is about 5micron. The resulting wettable powder is diluted with water before useto a spray liquor which may be applied by foliar spray as well as byroot drench application.

b. Granules

Onto 94.5 parts by weight of quartz sand in a tumbler mixer are sprayed0.5 parts by weight of a binder (non-ionic tenside) and the wholethoroughly mixed. 5 parts by weight of a compound of formula I inventionare then added and thorough mixing continued to obtain a granulateformulation with a particle size in the range of from 0.3 to 0.7 mm(where required, the granules may be dried by the addition of 1 to 5% byweight of talcum). The granules may be applied by incorporation into thesoil adjacent to the plants to be treated.

c. Emulsion Concentrate

10 Parts by weight of a compound of formula I are mixed with 10 parts ofweight of an emulsifier and 80 parts by weight of xylene. The thusobtained concentrate is diluted with water to form an emulsion of thedesired concentration, prior to application.

d. Seed Dressing

45 Parts of a compound of formula I are mixed with 1.5 parts of diamylphenoldecaglycolether ethylene oxide adduct, 2 parts of spindle oil, 51parts of fine talcum and 0.5 parts of colorant rhodanin B. The mixtureis ground in a contraplex mill at 10,000 rpm until an average particlesize of less than 20 microns is obtained. The resulting dry powder hasgood adherence and may be applied to seeds, e.g. by mixing for 2 to 5minutes in a slowly turning vessel.

The following examples further illustrate the present invention. Alltemperatures are in centigrade.

EXAMPLE 1 Methyl 2-2,4-dimethyl-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl!-3-methoxyacrylate##STR11## a) Methyl 2-2,4-dimethyl-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl!-acetate##STR12##

A mixture of methyl (4-chloro-2,6-dimethyl-5-pyrimidinyl)-acetate (5.0g, 23 mmol), 1-phenyl-1H-pyrazol-3-on (3.73 g, 23 mmol), potassiumcarbonate (5,5 g, 40 mmol) in dimethylformamide (30 ml) is heated at+120° C. for 2 hours. Addition of water, extraction with ether anddrying gives the intermediate methyl 2-2,4-dimethyl-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl!-acetate asa yellow oil.

¹ H-NMR (CDCl₃): 7.86 (d,1H); 7,67-7.20(m,5H); 6.32 (d,2H); 3.80 (s,2H);3.70 (s,3H); 2.57(s,3H); 2.36 (s,3H).

b) The intermediate methyl 2-2,4-dimethyl-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl!-acetate(6.8 g, 20 mmol), NaH (0.8 g of a 80% suspension in oil, 25 mmol) andN,N-diformylmethylamine (5 ml) in dimethylformamide (40 ml) is stirredat 45° C. for two hours. Dimethylsulfate (2.4 ml, 25 mmol) is added atroom temperature and stirring is continued for additional two hours.Dilution with ether, washing with brine, drying and chromatography onsilicagel (eluant: ethyl, acetate/hexane 1:1) gives methyl 2-2,4-dimethyl-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl!-3-methoxyacrylateas a colorless oil.

¹ H-NMR (CDCl₃): 7.86 (d,1H); 7.63 (s,1H); 7.67-7.20(m,5H); 6.32 (d,1H);3.88 (s,3H); 3.70 (s,3H); 2.57 (s,3H); 2.36 (s,3H).

EXAMPLE 2 Methyl 2-methoximino-2-methyl-4-dimethylamino-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl!-acetate##STR13## a) Methyl 2-2-methyl-4-dimethylamino-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl!-acetate##STR14##

A mixture of methyl (4,6-dichloro-2-methyl-pyrimidin-5-yl )-acetate(5.43 g, 23 mmol), 1-phenyl-1H-pyrazol-3-on (3.73 g, 23 mmol) andpotassium carbonate (5.5 g, 40 mmol) in dimethylformamide (30 ml) isheated at +120° C. for 30 minutes. Addition of dimethylamine (10 ml of a25% aqueous solution) at room temperature, stirring for 20 hours andworkup gives the intermediate methyl 2-2-methyl-4-dimethylamino-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl!-acetateas an oil.

b) Methyl 2-hydroximino-2-2-methyl-4-dimethylamino-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl!-acetate##STR15##

A solution of methyl 2-2-methyl-4-dimethylamino-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl!-acetate(8.0 g, 22 mmol) in dimethoxyethane (20 ml) is added to a solution oft-BuOK (7.3 g, 65 mmol) and t-BuONO (8 ml) in dimethoxyethane (80 ml) at40° C. After stirring for 30 minutes the mixture is quenched withammonium chloride (aqueous solution, 75 ml). The mixture is stirred fortwo hours. Extraction with ether, drying and chromatography on silicagel(eluant:ethyl acetate/hexane 1:1) gives the crystalline methyl2-hydroximino-2-2-methyl-4-dimethylamino-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl!-acetate.

c) The methyl 2-hydroximino-2-2-methyl-4-dimethylamino-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl!-acetate(3.5 g, 8.8 mmol) is added to a suspension of NaH (0.3 g, 10 mmol) indimethylformamide (30 ml) and dimethylsulfate (0.9 ml, 9.7 mmol). Themixture is stirred at room temperature for 2 hours. Dilution with etherwashing with brine, drying and chromatography on silicagel (eluant ethylacetate/hexane 1:1) gives methyl 2-methoximino-2-2-methyl-4-dimethylamino-6-(1-phenyl-1H-pyrazol-3-yloxy)-pyrimidin-5-yl!-acetate.

¹ H-NMR (CDCl₃): 7.82 (d,1H); 7.67-7.20(m,5H); 6.22 (d,2H); 4.06 (s,3H);3.88 (s,3H); 3.03 (s,6H); 2.41 (s,3H).

EXAMPLE 3 Methyl 2-2,4-dimethyl-(1-(2,6-dichlorobenzyl)-1H-pyrazol-3-yloxy)-pyrimidin-5-yl!-3-methoxy-acrylate##STR16## a) Methyl 2-2,4-dimethyl-6-(1-(2,6-dichlorobenzyl)-1H-pyrazol-3-yloxy)-pyrimidin-5-yl!-acetate##STR17##

A mixture of methyl (2,4-dimethyl-6-chloro-5-pyrimidinyl)-acetate (0.5g, 23 mmol), 1-(2,6-dichlorobenzyl)-1H-pyrazol-3-on (5.80 g, 23 mmol)and potassium carbonate (10.0 g, 70 mmol) in dimethylformamide (30 ml)is heated at +130° C. for 2 hours. Addition of water, extraction withether and drying gives the intermediate methyl 2-2,4-dimethyl-6-(1-(2,6-dichlorobenzyl)-1H-pyrazol-3-yloxy)-pyrimidin-5-yl!-acetateas a yellow oil.

b) The intermediate methyl 2-2,4-dimethyl-6-(1-(2,6-dichlorobenzyl)-1H-pyrazol-3-yloxy)-pyrimidin-5-yl!-acetate(9,6 g, 23 mmol) is dissolved in dimethylformamide (20 ml) and added at+30° C. to a suspension of NaH (1.3 g, of a 80% suspension in oil, 46mmol) and N,N-diformylmethylamine (10 ml) in dimethylformamide (40 ml).The mixture is stirred for 2 hours at +45° C. Dimethylsulfate (2,4 ml,25 mmol) is added at room temperature with cooling and stirring iscontinued for additional two hours. Dilution with ether, washing withbrine, drying and chromatography on silicagel (eluant:ethylacetate/hexane 3:1) gives methyl 2-2,4-dimethyl-6-(1-(2,6-dichlorobenzyl)-1H-pyrazol-3-yloxy)-pyrimidin-5-yl!-3-methoxyacrylateas a colorless oil (4.8 g).

¹ H-NMR (CDCl₃): 7.59(s,1H); 7.39-7.23(m,3H); 7.19(d,1H); 6.04(d,1H);5.54(s,2H); 3.83(s,3H); 3.67(s,3H); 2.53(s,3H); 2.33(s,3H).

EXAMPLE 4 Methyl 2-2,4-dimethyl-6-(1-(2-methylphenyl)-1H-pyrazol-4-yloxy)-pyrimidin-5-yl!-3-methoxyacrylate##STR18## a) Methyl 2-2,4-dimethyl-6-(1-(2-methylphenyl)-1H-pyrazol-4-yloxy)-pyrimidin-5-yl!-acetate##STR19##

A mixture of methyl (4-chloro-2,6-dimethyl-5-pyrimidinyl)-acetate (4.6g, 21 mmol), 1-(2-methylphenyl)-1H-pyrazol-4-on (4.1 g, 23 mmol) andpotassium carbonate (6.4 g, 46 mmol) in dimethylformamide (50 ml) isheated at +120° C. for 2 hours. Addition of water, extraction with etherand drying gives the intermediate methyl 2-2,4-dimethyl-6-(1-(2-methylphenyl)-1H-pyrazol4-yloxy)-pyrimidin-5-yl!-acetateas an oil.

¹ H-NMR (CDCl₃): 7.23-7.96(m, 6H); 3.78(s, 2H); 3.73(s,3H); 2.58(s,3H);2.47(s, 3H); 2.29 (s,3H).

b) The intermediate methyl 2-2,4-dimethyl-6-(1-(2-methylphenyl)-1H-pyrazol-4-yloxy)-pyrimidin-5-yl!-acetate(6.0 g, 17 mmol), sodium hydride (0.9 g, 37 mmol) andN,N-diformylmethylamine (6 ml) in a mixture of dimethylformamide (20 ml)and 1,2-dimethoxyethane (20 ml) is stirred at 45° C. for 3 hours.Methyliodide (4.2 g, 30 mmol) is added at room temperature and stirringis continued for additional 16 hours. Dilution with ether, washing withbrine, drying and chromatography on silicagel (eluant ethylacetate/hexane 3:7) gives methyl 2-2,4-dimethyl-6-(1-(2-methylphenyl)-1H-pyrazole-4-yloxy)-pyrimidin-5-yl!-3-methoxyacrylateas a colorless oil.

¹ H-NMR(CDCl₃): 7.26-7.95(m,6H); 3.90(s,3H); 3.74(s,3H); 2.59(s,3H);2.38(s,3H) 2.33(s,3H).

EXAMPLE 5 1-(2,5-Dichlorophenyl)-2-pyrazolone ##STR20## a)1-(2,5-Dichlorophenyl)-3-pyrazolidone ##STR21##

2,5-Dichlorophenylhydrazine hydrochloride (240 g, 1.1 mol) andacrylamide (100 g, 1.4 mol) is refluxed in a solution of sodium (56 g,2.4 mol) in ethanol (1000 ml) and toluene (1000 ml) for 3 hours.Evaporation of the solvents, acidification with acetic acid dilutionwith water, filtration and drying (high vacuum, +100° C.) gives the1-(2,5-dichlorophenyl)-3-pyrazolidone.

b) Hydrogen peroxide (30% solution in water, 120 ml) is slowly added toa well stirred suspension of 1-(2,5-dichlorophenyl)-3-pyrazolidone (200g, 0.86 mol) and selenium dioxide (3.0 g) in acetic acid (1000 ml). Thetemperature is controlled by cooling, not to exceed +50° C. Afterstirring at this temperature for 1 hour crushed ice and water is added.The product is filtered and dried yielding1-(2,5-dichlorophenyl)-3-pyrazolone, m.p. 201°-202° C.

EXAMPLE 6 1-Phenyl-3-pyrazolidone ##STR22##

Phenylhydrazine (10.8 g, 0.1 mol), and acrylamide (7.8 g, 0.11 mol),pulverized potassium hydroxide (12.5 g, 0.22) and a catalytic amount oftetrabutylammonium bromide is refluxed for 30 minutes. The precipitateis filtered and washed with toluene. The crystalline sold is dissolvedin water. Acidification with acetic acid, filtration and drying gives1-phenyl-3-pyrazolidone.

The compounds of the following tables are obtained in analogous manner:

                                      TABLE 1                                     __________________________________________________________________________     ##STR23##                                                                                                  physical data                                   Comp.                         .sup.1 HNMR (CDCl.sub.3) or/and                 No. R.sub.1                                                                            R.sub.2                                                                            R.sub.3                                                                          R.sub.4      m.p.                                            __________________________________________________________________________    1.01                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2,3-dichlorophenyl                                                                         7.58(s, 1H); 7.57-                                                            7.27(m, 3H); 6.17(s, 1H);                                                     3.85(s, 3H); 3.70(s, 3H);                                                     2.62(s, 3H); 2.32(s, 3H);                                                     2.18(s, 3H).                                                                  m.p. 169-171° C.                         1.02                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-chlorophenyl                                                                             7.58(s, 1H); 7.54-                                                            7.30(m, 4H); 6.17(s, 1H);                                                     3.85(s, 3H); 3.70(s, 3H);                                                     2.58(s, 3H); 2.35(s, 3H);                                                     2.18(s, 3H).                                                                  m.p. 135-137° C.                         1.03                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2,4-dichlorophenyl                                                                         7.59(s, 1H); 7.55-                                                            7.25(m, 3H); 6.12(s, 1H);                                                     3.85(s, 3H); 3.65(s, 3H);                                                     2.58(s, 3H); 2.33(s, 3H);                                                     2.17(s, 3H).                                    1.04                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2,5-dichlorophenyl                                                                         7.59(s, 1H); 7.49-                                                            7.35(m, 3H); 7.24(s, 1H);                                                     6.14(s, 1H); 3.85(s, 3H);                                                     3.68(s, 3H); 2.58(s, 3H);                                                     2.32(s, 3H); 2.18(s, 3H).                                                     m.p. 142-144° C.                         1.05                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2,6-dichlorophenyl                                                                         7.59(s, 1H); 7,47-                                                            7.23(m, 3H); 6.18(s, 1H);                                                     3.83(s, 3H); 3.68(s, 3H);                                                     2.57(s, 3H); 2.33(s, 3H);                                                     2.12(3, 3H).                                    1.06                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2,4,5-       7.65(s, 1H); 7.62-                                               trichlorophenyl                                                                            7.40(m, 2H); 6.14(s, 1H);                                                     3.86(s, 3H); 3.69(s, 3H);                                                     2.58(s, 3H); 2.34(s, 3H);                                                     2.18(s, 3H).                                    1.07                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2,4,6-       7.59(s, 1H); 7.43(s, 2H);                                        trichlorophenyl                                                                            6.18(s, 1H); 3.84(s, 3H);                                                     3.68(s, 3H); 2.55(s, 3H);                                                     2.33(s, 3H); 2.12(s, 3H).                       1.08                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-CF.sub.3 -phenyl                                                                         7.52(s, 1H); 7.76-7.34                                                        (m, 3H); 6.06(s, 1H);                                                         3.79(s, 3H); 3.63(s, 3H);                                                     2.52(s, 3H); 2.29(s, 3H);                                                     2.04(s, 3H).                                                                  m.p. 143-144° C.                         1.09                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-fluorophenyl                                                                             7.59(s, 1H); 7.52-                                                            7.18(m, 3H); 6.13(s, 1H);                                                     3.87(s, 3H); 3.70(s, 3H);                                                     2.59(s, 3H); 2.34(s, 3H);                                                     2.22(s, 3H).                                    1.10                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-methyl-5-  7.59(s, 1H); 7.34-                                               chlorophenyl 7.22(m, 3H); 6.10(s, 1H);                                                     3.86(s, 3H); 3.69(s, 3H);                                                     2.58(s, 3H); 2.33(s, 3H);                                                     2.09(s, 3H).                                                                  m.p. 139-141° C.                         1.11                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         phenyl       7.59(s, 1H); 7.48-                                                            7.32(m, 5H); 6.09(s, 1H);                                                     3.85(s, 3H); 3.69(s, 3H);                                                     2.58(s. 3H); 2.33(s, 3H);                                                     2.22(s, 3H).                                    1.12                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  phenyl       7.86(d, 1H); 7.63(s, 1H);                                                     7.67-7.20(m, 5H);                                                             6.32(d, 2H); 3.88(s, 3H);                                                     3.70(s, 3H); 2.57(s, 3H);                                                     2.36(s, 3H).                                    1.13                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  2-chlorophenyl                                                                             7.86(d, 1H); 7.63(s, 1H);                                                     7.67-7.24(m, 5H);                                                             6.37(d, 2H); 3.88(s, 3H);                                                     3.74(s, 3H); 2.58(s, 3H);                                                     2.37(s, 3H).                                                                  m.p. 150-15l° C.                         1.14                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  2,4-dichlorophenyl                                                                         7.82(d, 1H); 7.60(s, 1H);                                                     7.58-7.30(m, 3H);                                                             6.37(d, 1H); 3.87(s, 3H);                                                     3.70(s, 3H); 2.58(s, 3H);                                                     2.37(s, 3H).                                    1.15                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  2-fluorophenyl                                                                             7.97(d, 1H); 7.92-                                                            7.17(m, 4H); 7.62(s, 1H);                                                     6.33(d, 1H); 3.90(s, 3H);                                                     3.72(s, 3H); 2.58(s, 3H);                                                     2.37(s.3H).                                                                   m.p. 150-151° C.                         1.16                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  benzyl       7.59(s, 1H); 7.38-                                                            7.20(m, 6H); 6.09(d, 1H);                                                     5.22(s, 2H); 3.87(s, 3H);                                                     3.70(s, 3H); 2.57(s, 3H);                                                     2.33(s, 3H).                                                                  m.p. 130-131° C.                         1.17                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  2,6-dichlorobenzyl                                                                         7.59(s, 1H); 7.39-                                                            7.23(m, 3H); 7.19(d, 1H);                                                     6.04(d, 1H); 5.54(s, 2H);                                                     3.83(s, 3H); 3.67(s, 3H);                                                     2.53(s, 3H); 2.33(s, 3H).                       1.18                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H                                                                                 ##STR24##   7.59(s, 1H); 7.30- 6.93(m, 4H); 6.08(d,                                       1H); 5.34(s, 2H); 3.85(s, 3H); 3.69(s, 3H);                                   2.53(s, 3H); 2.33(s, 3H). m.p.                                                115-117° C.                              1.19                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  3-methoxybenzyl                                                                            7.59(s, 1H); 7.24(d, 1H);                                                     7.22-6.78(m, 4H);                                                             6.07(d, 1H); 5.17(s, 2H);                                                     3.84(s, 3H); 3.78(s, 3H);                                                     3.70(s, 3H); 2.57(s, 3H);                                                     2.35(s, 3H).                                    1.20                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  4-methoxybenzyl                                                                            7.60(s, 1H); 7.24(d, 1H);                                                     7.22-6.84(m, 4H);                                                             6.07(d, 1H); 5.15(s, 2H);                                                     3.85(s, 3H); 3.80(s, 3H);                                                     3.70(s, 3H); 2.56(s, 3H);                                                     2.35(s, 3H).                                    1.21                                                                              CH.sub.3                                                                           N(CH.sub.3).sub.2                                                                  H  phenyl                                                       1.22                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-cyanophenyl                                                                              7.80-7.48(m, 4H);                                                             7.59(s, 1H); 6.20(s, 1H);                                                     3.85(s, 3H); 3.70(s, 3H);                                                     2.58(s, 3H); 2.37(s, 3H);                                                     2.30(s, 3H).                                                                  m.p. 154-156° C.                         1.23                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-chlorophenyl                                                                             7.60(s, 1H); 7.52-                                                            7.32(m, 4H); 6.10(s, 1H);                                                     3.85(s, 3H); 3.69(s, 3H);                                                     2.58(s, 3H); 2.39(s, 3H);                                                     2.37(s, 3H).                                                                  m.p. 135-136° C.                         1.24                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-CF.sub.3 -phenyl                                                                         7.79-7.57(m, 4H);                                                             7.59(s, 1H); 6.13(s, 1H);                                                     3.87(s, 3H); 3.70(s, 3H);                                                     2.58(s, 3H); 2.40(s, 3H);                                                     2.37(s, 3H).                                    1.25                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-nitrophenyl                                                                              8.00(dd, 1H); 7.75-                                                           7.54(m, 3H); 7.59(s, 1H);                                                     6.16(s, 1H); 3.85(s, 3H);                                                     3.70(s, 3H); 2.59(s, 3H);                                                     2.37(s, 3H); 2.22(s, 3H).                                                     m.p. 110-111° C.                         1.26                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-methoxy-5- 7.59(s, 1H); 7.40-                                               chloro-phenyl                                                                              6.91(m, 3H); 6.08(s, 1H);                                                     3.86(s, 3H); 3.80(s, 3H);                                                     370(s, 3H); 2.60(s, 3H);                                                      2.37(s, 3H); 2.18(s, 3H).                                                     m.p. 140-141° C.                         1.27                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  2-methylphenyl                                                                             7.62(s, 1H); 7.50(d, 1H);                                                     7.38-7.22(m, 4H);                                                             6.33(d, 1H); 3.85(s, 3H);                                                     3.70(s, 3H); 2.57(s, 3H);                                                     2.36(s, 3H); 2.31(s, 3H).                                                     m.p. 160-161° C.                         1.28                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3,4-diclorophenyl                                                                          7.63-7.33(m, 3H);                                                             7.62(s, 1H); 6.12(s, 1H);                                                     3.86(s, 3H); 3.70(s, 3H);                                                     2.58(s, 3H); 2.40(s, 3H);                                                     2.37(s, 3H).                                                                  m.p. 126-129° C.                         1.29                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-nitrophenyl                                                                              8.38-7.62(m, 4H);                                                             7.60(s, 1H); 6.17(s, 1H);                                                     3.88(s, 3H); 3.73(s, 3H);                                                     2.60(s, 3H); 2.47(s, 3H);                                                     2.37(s, 3H).                                                                  m.p. 146-147° C.                         1.30                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-CF.sub.3 -4-chloro-                                                                      7.83-7.57(m, 3H);                                                phenyl       7.60(s, 1H); 6.14(s, 1H);                                                     3.85(s, 3H); 3.70(s, 3H);                                                     2.58(s, 3H); 2.40(s, 3H);                                                     2.37(s, 3H).                                                                  m.p. 125-128° C.                         1.31                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          H  2-chlorophenyl                                                                             7.82(d, 1H); 7.63-                                                            7.23(m, 4H); 7.56(s, 1H);                                                     6.30(d, 1H); 3.97(s, 3H);                                                     3.82(s, 3H); 3.67(s, 3H);                                                     2.50(s, 3H)                                                                   m.p. 123-125° C.                         1.32                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         2-chlorophenyl                                                                             7.55(s, 1H); 7.54-                                                            7.30(m, 4H); 6.07(s, 1H);                                                     3.93(s, 3H); 3.80(s, 3H);                                                     3.64(s, 3H); 2.50(s, 3H);                                                     2.15(s, 3H).                                                                  m.p. 141-142° C.                         1.33                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          H  2-methoxybenzyl                                                                            7.53(s, 1H); 7.33-                                                            6.84(m, 5H); 6.02(d, 1H);                                                     5.20(s, 2H); 3.93(s, 3H);                                                     3.83(s, 3H); 3.80(s, 3H);                                                     3.67(s, 3H); 2.47(s, 3H).                                                     m.p. 110-112° C.                         1.34                                                                              C.sub.2 H.sub.5                                                                    OCH.sub.3                                                                          H  2-methoxybenzyl                                                                            7.55(s, 1H); 7.34-                                                            6.84(m, 5H); 6.07(d, 1H);                                                     3.93(s, 3H); 3.82(s, 3H);                                                     3.78(s, 3H); 3.69(s, 3H);                                                     2.75(q, 2H); 1.12(t, 3H).                                                     m.p. 80-82° C.                           1.35                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          H  2-chlorobenzyl                                                                             7.54(s, 1H); 7.39-                                                            7.02(m, 5H); 6.07(d, 1H);                                                     5.30(s, 2H); 3.93(s, 3H);                                                     3.80(s, 3H); 3.64(s, 3H);                                                     2.45(s, 3H).                                                                  m.p. 119-122° C.                         1.36                                                                              C.sub.2 H.sub.5                                                                    OCH.sub.3                                                                          H  2-chlorobenzyl                                                                             7.55(s, 1H); 7.38-                                                            7.00(m, 5H); 6.10(d, 1H);                                                     5.30(s, 2H); 3.94(s, 3H);                                                     3.80(s, 3H), 3.70(s, 3H);                                                     2.76(q, 2H); 1.24(t, 3H).                                                     m.p. 93-96° C.                           1.37                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  2-methoxybenzyl                                                                            7.59(s, 1H); 7.22(d, 1H);                                                     7.20-6.80(m, 4H);                                                             6.08(d, 1H); 5.14(s, 2H);                                                     3.85(s, 3H); 3.80(s, 3H);                                                     3.69(s, 3H); 2.54(s, 3H);                                                     2.33(s, 3H).                                    1.38                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  2,5-dichlorophenyl                                                                         7.90(d, 1H); 7.68-                                                            7.23(m, 3H); 7.61(s, 1H);                                                     6.37(d, 1H); 3.86(s, 3H);                                                     3.70(s, 3H); 2.58(s, 3H);                                                     2.37(s, 3H).                                                                  m.p. 144-145° C.                         1.39                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H                                                                                 ##STR25##   8.43(d, 1H); 7.77- 7.06(m, 3H); 7.62(s,                                       1H); 6.30(d, 1H); 3.87(s, 3H); 3.70(s, 3H);                                   3.55(s, 3H); 2.37(s, 3H). m.p.                                                127-129° C.                              1.40                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-methoxyphenyl                                                                            7.58(s, 1H); 7.34-                                                            6.85(m, 4H); 6.06(s, 1H);                                                     3.83(s, 3H); 3.80(s, 3H);                                                     3.70(s, 3H); 3.58(s, 3H);                                                     2.38(s, 3H); 2.37(s, 3H).                                                     m.p. 101-102° C.                         1.41                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  3-chlorophenyl                                                                             7.84(d, 1H); 7.70-                                                            7.18(m, 4H); 7.62(s, 1H);                                                     6.31(d, 1H); 3.88(s, 3H);                                                     3.70(s, 3H); 2.57(s, 3H);                                                     2.37(s, 3H).                                                                  m.p. 120-121° C.                         1.42                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3,5-dichlorophenyl                                                                         7.60(s, 1H); 7.42(d, 2H);                                                     7.33(d, 1H); 6.10(s, 1H);                                                     3.86(s, 3H); 3.70(s, 3H);                                                     2.58(s, 3H); 2.41(s, 3H);                                                     2.36(s, 3H),                                                                  m.p. 184-185° C.                         1.43                                                                              CH.sub.3                                                                           SCH.sub.3                                                                          H                                                                                 ##STR26##   8.43(d, 1H); 7.78- 7.13(m, 3H); 7.61(s,                                       1H); 6.27(d, 1H); 3.89(s, 3H); 3.70(s, 3H);                                   2.57(s, 3H); 2.56(s, 3H). m.p.                                                148-150° C.                              1.44                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          H  3-chlorophenyl                                                                             7.83(d, 1H); 7.70-                                                            7.17(m, 4H); 7.57(s, 1H);                                                     6.28(d, 1H); 3.94(s, 3H);                                                     3.83(s, 3H); 3.70(s, 3H);                                                     2.50(s, 3H);                                                                  m.p. 150-151° C.                         1.45                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          H                                                                                 ##STR27##   m.p. 133-135° C.                         1.46                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  3-cyanophenyl                                                1.47                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  4-biphenylyl                                                 1.48                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H                                                                                 ##STR28##   8.40(d, 1H); 7.88- 7.80(m, 2H); 7.63(s,                                       1H); 7.52-7.30(m, 2H); 6.41(d, 1H); 3.89(s,                                   3H); 3.73(s, 3H); 2.58(s, 3H); 2.38(s, 3H).                                   .p. 178-181° C.                          1.49                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H                                                                                 ##STR29##                                                   1.50                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  3,4-dichlorophenyl                                                                         7.80(d+s, 2H); 7.63(s, 1H);                                                   7.49(s, 2H); 6.35(d, 1H);                                                     3.89(s, 3H); 3.70(s, 3H);                                                     2.58(s, 3,11); 2.38(s, 3H).                                                   m.p. 192-194° C.                         1.51                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  3-CF.sub.3 -phenyl                                                                         7.96-7.47(m, 4H);                                                             7.90(d, 1H); 7.63(s, 1H);                                                     6.37(d, 1H); 3.89(s, 3H);                                                     3.70(s, 3H); 3.57(s, 3H);                                                     2.38(s, 3H),                                                                  m.p. 130° C.                             1.52                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  3-methoxyphenyl                                              1.53                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H                                                                                 ##STR30##                                                   1.54                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  2-nitrophenyl                                                1.55                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  3-nitrophenyl                                                1.56                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  2,6-dichlorophenyl                                           1.57                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         5-CF.sub.3 -2-chloro-                                                         phenyl                                                       1.58                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         4-biphenylyl                                                 1.59                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                          ##STR31##                                                   1.60                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                          ##STR32##                                                   1.61                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3,4-                                                                          dimethoxyphenyl                                              1.62                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-pyridyl                                                    1.63                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         4-phenoxyphenyl                                              1.64                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  2-methyl-5-chloro-                                                                         7.62(s, 1H); 7.53(d, 1H);                                        phenyl       7.28-7.19(m, 3H);                                                             6.33(d, 1H); 3.86(s, 3H);                                                     3.70(s, 3H); 2.58(s, 3H);                                                     2.38(s, 3H); 2.34(s, 3H).                                                     m.p. 122-123° C.                         1.65                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  4-chlorophenyl                                                                             7.82(d, 1H); 7.60(s, 1H);                                                     7.58-7.38(m, 4H);                                                             6.34(d, 1H); 3.88(s, 3H);                                                     3.70(s, 3H); 2.59(s, 3H);                                                     2.39(s, 3H).                                    1.66                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-fluorophenyl                                                                             7.60(s, 1H); 7.42-                                                            6.97(m, 4H); 6.08(s, 1H);                                                     3.86(s, 3H); 3.70(s, 3H);                                                     2.58(s, 3H); 2.38(s, 3H);                                                     2.37(s, 3H).                                                                  m.p. 129-130° C.                         1.67                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                          ##STR33##   7.78(s, 1H); 7.65- 7.40(m, 4H); 6.09(s,                                       1H); 3.97(s, 3H); 3.86(s, 3H); 3.70(s, 3H);                                   2.60(s, 3H); 2.39(2×s, 6H); 2.26(s,                                     3H).                                            1.68                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         4-fluorophenyl                                                                             7.60(s, 1H); 7.43-                                                            7.03(m, 4H); 6.08(s, 1H);                                                     3.85(s, 3H); 3.70(s, 3H);                                                     2.60(s, 3H); 2.38(s, 3H);                                                     2.37(s, 3H).                                    1.69                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         4-chlorophenyl                                                                             7.60(s, 1H); 7.41(s, 4H);                                                     6.06(s, 1H); 3.87(s, 3H);                                                     3.70(s, 3H); 2.59(s, 3H);                                                     2.38(2s, 6H)                                    1.70                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          H  3,4-dichlorophenyl                                                                         7.80(d+s, 2H); 7.58(s, 1H);                                                   7.49(s, 2H); 6.33(d, 1H);                                                     3.97(s, 3H); 3.85(s, 3H);                                                     3.70(s, 3H); 2.50(s, 3H).                                                     m.p. 157-159° C.                         1.71                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         3-CF.sub.3 -phenyl                                                                         7.80-7.53(m, 5H);                                                             6.05(s, 1H); 3.95(s, 3H);                                                     3.83(s, 3H); 3.70(s, 3H);                                                     2.52(s, 3H); 2.38(s, 3H).                                                     m.p. 109-111° C.                         1.72                                                                              N(CH.sub.3).sub.2                                                                  CH.sub.3                                                                           H  3-chlorophenyl                                                                             7.81(d, 1H); 7.70-                                                            7.17(m, 5H); 7.37(d, 1H);                                                     3.85(s, 3H); 3.70(s, 3H);                                                     3.04(s, 6H); 2.23(s, 3H).                                                     m.p. 163-165° C.                         1.73                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          H  3-CF.sub.3 -phenyl                                                                         7.96-7.47(m, 6H);                                                             6.33(d, 1H); 3.96(s, 3H);                                                     3.86(s, 3H); 3.70(s, 3H);                                                     2.50(s, 3H).                                                                  m.p. 152-154° C.                         1.74                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          H  2,5-dichlorophenyl                                                                         7.90(d, 1H); 7.70-                                                            7.23(m, 4H); 6.33(d, 1H);                                                     3.96(s, 3H); 3.84(s, 3H);                                                     3.70(s, 3H); 2.53(s, 3H).                       1.75                                                                              H    CH.sub.3                                                                           H  3-CF.sub.3 -phenyl                                                                         8.64(s, 1H); 7.95(d, 1H);                                                     7.82-7.50(m, 5H);                                                             6.33(d, 1H); 3.93(s, 3H);                                                     3.73(s, 3H); 2.42(s, 3H).                                                     m.p. 153-155° C.                         1.76                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          H  5-chloro-2-  7.57(s, 1H); 7.50(d, 1H);                                        methylphenyl 7.40-7.18(m, 3H);                                                             6.28(d, 1H); 3.95(s, 1H);                                                     3.83(s, 3H); 3.70(s, 3H);                                                     2.50(s, 3H); 2.32(s, 3H).                                                     m.p. 102-106° C.                         1.77                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-chloro-2-  7.60(s, 1H); 7.46-                                               methylphenyl 7.19(m, 3H); 6.08(s, 1H);                                                     3.83(s, 3H); 3.70(s, 3H);                                                     2.58(s, 3H); 2.37(s, 3H);                                                     2.10(2s, 6H).                                                                 m.p. 157-159° C.                         1.78                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         4-chloro-2-  7.60(s, 1H); 7.32-                                               methylphenyl 7.20(m, 3H); 6.04(s, 1H);                                                     3.84(s, 3H); 3.70(s, 3H);                                                     2.57(s, 3H); 2.36(s, 3H);                                                     2.10(2s, 6H).                                   1.79                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         3-chlorophenyl                                                                             7.56(s, 1H); 7.50-                                                            7.26(m, 4H); 6.04(s, 1H);                                                     3.93(s, 3H); 3.83(s, 3H);                                                     3.68(s, 3H); 2.53(s, 3H);                                                     2.38(s, 3H).                                    1.80                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         4-chlorophenyl                                                                             7.52(s, 1H); 7.38(s, 4H);                                                     6.03(s, 1H); 3.94(s, 3H);                                                     3.82(s, 3H); 3.66(s, 3H);                                                     2.51(s, 3H); 2.36(s, 3H).                       1.81                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         3,4-dichlorophenyl                                                                         7.63-7.30(m, 4H);                                                             6.05(s, 1H); 3.93(s, 3H);                                                     3.82(s, 3H); 3.67(s, 3H),                                                     2.53(s, 3H); 2.38(s, 3H).                                                     m.p. 147-148° C.                         1.82                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         2,3-dichlorophenyl                                                                         7.60-7.27(m, 4H);                                                             6.08(s, 1H); 3.92(s, 3H);                                                     3.81(s, 3H); 3.64(s, 3H);                                                     2.50(s, 3H); 2.15(s, 3H).                                                     m.p. 147-150° C.                         1.83                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         3,5-dichlorophenyl                                                                         7.52(s, 1H); 7.40-                                                            7.28(m, 3H); 6.03(s, 1H);                                                     3.93(s, 3H); 3.80(s, 3H);                                                     3.66(s, 3H); 2.48(s, 3H);                                                     2.38(s, 3H).                                                                  m.p. 160-161° C.                         1.84                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         4-chloro-2-  7.52(s, 1H); 7.32-                                               methylphenyl 7.20(m, 3H); 6.02(s, 1H);                                                     3.90(s, 3H); 3.83(s, 3H);                                                     3.67(s, 3H); 2.50(s, 3H);                                                     2.15(2s, 6H).                                                                 m.p. 140-143° C.                         1.85                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         3-chloro-2-  7.52(s, 1H); 7.45-                                               methylphenyl 7.20(m, 3H); 6.03(s, 1H);                                                     3.93(s, 3H); 3.82(s, 3H);                                                     3.68(s, 3H); 2.50(s, 3H);                                                     2.15(s, 3H); 2.14(s, 3H).                                                     m.p. 147-149° C.                         1.86                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         2,4-dichlorophenyl                                                                         7.52-7.30(m, 4H);                                                             6.08(s, 1H); 3.95(s, 3H);                                                     3.80(s, 3H); 3.68(s, 3H);                                                     2.53(s, 3H); 2.17(s, 3H).                       1.87                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         5-chloro-2-  7.54(s, 1H); 7.34-                                               methylphenyl 7.20(m, 3H); 6.03(s, 1H);                                                     3.92(s, 3H); 3.80(s, 3H);                                                     3.67(s, 3H); 2.52(s, 3H);                                                     2.15(2s, 6H).                                   1.88                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-bromophenyl                                                                              7.65-7.30(m, 5H);                                                             6.10(s, 1H); 3.87(s, 3H);                                                     3.70(s, 3H); 2.59(s, 3H),                                                     2.38(s, 3H); 1.36(s, 3H);                                                     m.p. 141-142° C.                         1.89                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         4-bromophenyl                                                                              7.60(s, 1H); 7.57-                                                            7.30(m, 4H); 6.10(s, 1H);                                                     3.85(s, 3H); 3.70(s, 3H);                                                     2.58(s, 3H); 2.38(2s, 6H).                      1.90                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         3-bromophenyl                                                                              7.64-7.26(m, 5H);                                                             6.06(s, 1H); 3.97(s, 3H);                                                     3.83(s, 3H); 3.69(s, 3H);                                                     2.53(s, 3H); 2.38(s, 3H).                       1.91                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          H  3-bromophenyl                                                                              7.86-7.24(m, 5H);                                                             6.30(d, 1H); 3.97(s, 3H);                                                     3.86(s, 3H); 3.70(s, 3H);                                                     2.53(s, 3H).                                                                  m.p. 144-145° C.                         1.92                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          H  4-methylphenyl                                                                             7.78(d, 1H); 7.57-                                                            7.17(m, 5H); 6.23(d, 1H);                                                     3.97(s, 3H); 3.88(s, 3H);                                                     3.70(s, 3H); 2.52(s, 3H);                                                     2.38(s, 3H).                                    1.93                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  4-bromophenyl                                                                              7.80(d, 1H); 7.57(s, 1H);                                                     7.55(s, 4H); 6.28(d, 1H);                                                     3.97(s, 3H); 3.86(s, 3H);                                                     3.70(s, 3H); 2.53(s, 3H).                       1.94                                                                              CH.sub.3                                                                           OCH.sub.3                                                                          H  2,5-dimethylphenyl                                                                         7.56(s, 1H); 7.48(d, 1H);                                                     7.08-7.02(m, 3H);                                                             6.23(d, 1H); 3.96(s, 3H);                                                     3.84(s, 3H); 3.70(s, 3H);                                                     2.52(s, 3H); 2.38(s, 3H);                                                     2.25(s, 3H).                                                                  m.p. 86-87° C.                           1.95                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  3-bromophenyl                                                                              7.84(d, 1H); 7.62(s, 1H);                                                     7.57-7.26(m, 4H);                                                             6.33(d, 1H); 3.87(s, 3H);                                                     3.70(s, 3H); 2.58(s, 3H);                                                     2.38(s, 3H).                                                                  m.p. 120-122° C.                         1.96                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  4-bromophenyl                                                                              7.83(d, 1H); 7.63(s, 1H);                                                     7.53(s, 4H); 6.33(d, 1H);                                                     3.87(s, 3H); 3.70(s, 3H);                                                     2.58(s, 3H); 2.38(s, 3H).                                                     m.p. 141-142° C.                         1.97                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  4-methylphenyl                                                                             7.81(d, 1H); 7.62(s, 1H);                                                     7.50-7.19(m, 4H);                                                             6.29(d, 1H); 3.87(s, 3H);                                                     3.70(s, 3H); 2.58(s, 3H);                                                     2.38(2s, 6H),                                                                 m.p. 121-122° C.                         1.98                                                                              CH.sub.3                                                                           CH.sub.3                                                                           H  2,5-dimethylphenyl                                                                         7.60(s, 1H); 7.52(d, 1H);                                                     7.17-7.03(m, 3H);                                                             6.28(d, 1H); 3.84(s, 3H);                                                     3.70(s, 3H); 2.58(s, 3H);                                                     2.38(s, 3H); 2.37(s, 3H);                                                     2.30(s, 3H).                                    1.99                                                                              CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3,5-dimethylphenyl                                                                         7.60(s, 1H); 7.06(s, 2H);                                                     6.96(s, 1H); 6.06(s, 1H);                                                     3.84(s, 3H); 3.70(s, 3H);                                                     2.59(s, 3H); 2.37(4s;                                                         12H). m.p. 143-144° C.                   __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR34##                                                                                             physical data                                        Comp.                    .sup.1 HNMR (CDCl.sub.3) or/and                      No. R.sub.1                                                                          R.sub.2                                                                            R.sub.3                                                                          R.sub.4   m.p.                                                 __________________________________________________________________________    2.01                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         2,3-dichlorophenyl                                             2.02                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         2-chlorophenyl                                                 2.03                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         2,4-dichlorophenyl                                             2.04                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         2,5-dich1orophenyl                                             2.05                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         2,6-dichlorophenyl                                             2.06                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         2,4,5-trich1orophenyl                                          2.07                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         2,4,6-trichlorophenyl                                          2.08                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         2-CF.sub.3 -phenyl                                             2.09                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         2-fluorophenyl                                                 2.10                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         2-methyl-5-                                                                   chlorophenyl                                                   2.11                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         phenyl    7.48-7.32(m, 5H);                                                             6.14(s, 1H); 3.80(s, 2H);                                                     3.69(s, 2H); 2.55(s, 3H);                                                     2.45(s, 3H); 2.37(s, 3H).                            2.12                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H  phenyl                                                         2.13                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H  2-chlorophenyl                                                 2.14                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H  2,4-dich1orophenyl                                             2.15                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H  2-fluorophenyl                                                                          7.97(d, 1H); 7.90-                                                            7.14(m, 4H); 6.30(d, 1H);                                                     3.86(s, 2H); 3.70(s, 3H);                                                     2.57(s, 3H); 2.37(s, 3H).                            2.16                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H  benzyl                                                         2.17                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H  2,6-dichlorobenzyl                                             2.18                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H                                                                                 ##STR35##                                                     2.19                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H  3-methoxybenzyl                                                2.20                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H  4-methoxybenzyl                                                2.21                                                                              CH.sub.3                                                                         N(CH.sub.3).sub.2                                                                  H  phenyl    7.82(d, 1H); 7.67-                                                            7.20(m, 5H); 6.22(d, 2H);                                                     4.06(s, 3H); 3.88(s, 3H);                                                     3.03(s, 6H); 2.41(s, 3H).                            2.22                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         2-cyanophenyl                                                  2.23                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         3-chlorophenyl                                                 2.24                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         3-CF.sub.3 -phenyl                                             2.25                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         2-nitrophenyl                                                  2.26                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         2-methoxy-5-chloro-                                                           phenyl                                                         2.27                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H  2-methylphenyl                                                 2.28                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         3,4-dichlorophenyl                                             2.29                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         3-nitrophenyl                                                  2.30                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         3-CF.sub.3 -4-chloro-                                                         phenyl                                                         2.31                                                                              CH.sub.3                                                                         OCH.sub.3                                                                          H  2-chlorophenyl                                                 2.32                                                                              CH.sub.3                                                                         OCH.sub.3                                                                          CH.sub.3                                                                         2-chlorophenyl                                                 2.33                                                                              CH.sub.3                                                                         OCH.sub.3                                                                          H  2-methoxybenzyl                                                2.34                                                                              C.sub.2 H.sub.5                                                                  OCH.sub.3                                                                          H  2-methoxybenzyl                                                2.35                                                                              CH.sub.3                                                                         OCH.sub.3                                                                          H  2-chlorobenzyl                                                 2.36                                                                              C.sub.2 H.sub.5                                                                  OCH.sub.3                                                                          H  2-chlorobenzyl                                                                          7.40-7.03(m, 5H);                                                             6.12(d, 1H); 5.30(s, 2H);                                                     3.95(s, 3H); 3.85(s, 2H);                                                     3.70(s, 3H); 2.75(q, 2H);                                                     1.24(t, 3H).                                         2.37                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H  2-methoxybenzyl                                                2.38                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H  2,5-dichlorophenyl                                             2.39                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H                                                                                 ##STR36##                                                     2.40                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         3-methoxyphenyl                                                2.41                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H  3-chlorophenyl                                                 2.42                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         3,5-dichlorophenyl                                             2.43                                                                              CH.sub.3                                                                         SCH.sub.3                                                                          H                                                                                 ##STR37##                                                     2.44                                                                              CH.sub.3                                                                         OCH.sub.3                                                                          H  3-chlorophenyl                                                 2.45                                                                              CH.sub.3                                                                         OCH.sub.3                                                                          H                                                                                 ##STR38##                                                     2.46                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H  3-cyanophenyl                                                  2.47                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H  4-biphenylyl                                                   2.48                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H                                                                                 ##STR39##                                                     2.49                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H                                                                                 ##STR40##                                                     2.50                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H  3,4-dichlorophenyl                                             2.51                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H  3-CF.sub.3 -phenyl                                             2.52                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H  3-methoxyphenyl                                                2.53                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H                                                                                 ##STR41##                                                     2.54                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H  2-nitrophenyl                                                  2.55                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H  3-nitrophenyl                                                  2.56                                                                              CH.sub.3                                                                         CH.sub.3                                                                           H  2,6-dichlorophenyl                                             2.57                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         5-CF.sub.3 -2-chloro-                                                         phenyl                                                         2.58                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         4-biphenylyl                                                   2.59                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                          ##STR42##                                                     2.60                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                          ##STR43##                                                     2.61                                                                              CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                         3,4-dimethoxyphenyl                                            __________________________________________________________________________

                  TABLE 3                                                         ______________________________________                                         ##STR44##                                                                                                    physical data                                 Comp.                           .sup.1 HNMR (CDCl.sub.3)                      No.   R.sub.1                                                                              R.sub.2 R.sub.4    or/and m.p.                                   ______________________________________                                        3.01  CH.sub.3                                                                             CH.sub.3                                                                              2,3-dichlorophenyl                                                                       7.22-8.19(m, 5H);                                                             3.92(s, 3H); 3.76(s, 3H);                                                     2.62(s, 3H); 2.37(s, 3H).                     3.02  CH.sub.3                                                                             CH.sub.3                                                                              2-chlorophenyl                                                                           7.26-8.21(m, 6H);                                                             3.93(s, 3H); 3.76(s, 3H);                                                     2.62(s, 3H); 2.38(s, 3H).                     3.03  CH.sub.3                                                                             CH.sub.3                                                                              2,4-dichlorophenyl                                                                       7.28-8.20(m, 5H);                                                             3.91(s, 3H); 3.77(s, 3H);                                                     2.61(s, 3H); 2.38(s, 3H).                     3.04  CH.sub.3                                                                             CH.sub.3                                                                              2,5-dichlorophenyl                                                                       7.24-8.23(m, 5H);                                                             3.93(s, 3H); 3.78(s, 3H);                                                     2.59(s, 3H); 2.37(s, 3H).                     3.05  CH.sub.3                                                                             CH.sub.3                                                                              2,6-dichlorophenyl                                                                       7.26-7.97(m, 5H);                                                             3.88(s, 3H); 3.75(s, 3H);                                                     2.60(s, 3H); 2.37(s, 3H).                     3.06  CH.sub.3                                                                             CH.sub.3                                                                              2-methylphenyl                                                                           7.26-7.95(m, 6H);                                                             3.90(s, 3H); 3.74(s, 3H);                                                     2.59(s, 3H); 2.38(s, 3H);                                                     2.33(s, 3H).                                  3.07  CH.sub.3                                                                             CH.sub.3                                                                              2-isopropylphenyl                                                                        7.24-7-96(m, 6H);                                                             3.94(s, 3H); 3.77(s, 3H);                                                     3.03(m, 1H);                                                                  2.59(s, 3H);                                                                  2.38(s, 3H); 1.23(s, 3H);                                                     1.20(s, 3H).                                  3.08  CH.sub.3                                                                             CH.sub.3                                                                              2-CF.sub.3 -phenyl                                                                       7.56-8.18(m, 6H);                                                             3.92(s, 3H); 3.73(s, 3H);                                                     2.63(s, 3H); 2.37(s, 3H);                     3.09  CH.sub.3                                                                             CH.sub.3                                                                              2-methoxyphenyl                                                                          7.03-8.28(m, 6H);                                                             3.90(s, 3H); 3.77(s, 3H);                                                     2.60(s, 3H); 2.38(s, 3H);                                                     2.04(s, 3H).                                  3.10  CH.sub.3                                                                             CH.sub.3                                                                              2-methyl-5-                                                                              7.22-7-93(m, 5H);                                                  chlorophenyl                                                                             3.90(s, 3H); 3.74(s, 3H);                                                     2.61(s, 3H); 2.38(s, 3H);                                                     2.31(s, 3H).                                  3.11  CH.sub.3                                                                             CH.sub.3                                                                              phenyl     7.24-8.21(m, 7H);                                                             3.92(s, 3H); 3.75(s, 3H);                                                     2.61(s, 3H); 2.38(s, 3H).                     3.12  CH.sub.3                                                                             CH.sub.3                                                                              3-methylphenyl                                                                           6.84-7.59(m, 6H);                                                             3.90(s, 3H); 3.74(s, 3H);                                                     2.51(s, 3H); 2.38(s, 3H).                     3.13  CH.sub.3                                                                             CH.sub.3                                                                              2-chloro-4-                                                                              7.16-8.13(m, 5H);                                                  methylphenyl                                                                             3.94(s, 3H); 3.78(s, 3H);                                                     2.59(s, 3H); 2.50(s, 3H);                                                     2.39(s, 3H).                                  3.14  CH.sub.3                                                                             CH.sub.3                                                                              2-cyano-4- 7.63-8.59(m, 5H);                                                  chlorophenyl                                                                             3.81(s, 3H); 3.76(s, 3H);                                                     2.62(s, 3H); 2.53(2, 3H).                     3.15  CH.sub.3                                                                             CH.sub.3                                                                              3-CF.sub.3 -phenyl                                                                       7.49-8.21(m, 6H);                                                             3.92(s, 3H); 3.74(s, 3H);                                                     2.63(s, 3H); 2.38(s, 3H).                     3.16  CH.sub.3                                                                             CH.sub.3                                                                              4-chlorophenyl                                                                           7.39-8.12(m, 6H);                                                             3.89(s, 3H); 3.72(s, 3H);                                                     2.61(s, 3H); 2.37(s, 3H);                     3.17  CH.sub.3                                                                             CH.sub.3                                                                              2-cyanophenyl                                                                            7.40-8.58(m, 6H);                                                             3.92(s, 3H); 3.75(s, 3H);                                                     2.62(s, 3H); 2.37(s, 3H).                     3.18  CH.sub.3                                                                             CH.sub.3                                                                              2-methyl-3-                                                                              7.20-7.89(m, 5H);                                                  chlorophenyl                                                                             3.92(s, 3H); 3.74(s, 3H);                                                     2.59(s, 3H); 2.37(s, 3H);                                                     2.28(s, 3H).                                  3.19  CH.sub.3                                                                             CH.sub.3                                                                              2-methyl-4-                                                                              7.22-7.87(m, 5H);                                                  chlorophenyl                                                                             3.93(s, 3H); 3.76(s, 3H);                                                     2.60(s, 3H); 2.39(s, 3H);                                                     2.34(s, 3H).                                  3.20  CH.sub.3                                                                             CH.sub.3                                                                              2.3-dimethylphenyl                                                                       7.17-7.86(m, 5H);                                                             3.91(s, 3H); 3.76(s, 3H);                                                     2.60(s, 3H); 2.38(s, 6H);                                                     2.15(s, 3H).                                  3.21  CH.sub.3                                                                             CH.sub.3                                                                              2,6-dimethylphenyl                                                                       7.06-7.64(m, 5H);                                                             3.91(s, 3H); 3.73(s, 3H);                                                     2.44(s, 3H); 2.37(s, 3H);                                                     2.08(s, 6H).                                  3.22  CH.sub.3                                                                             CH.sub.3                                                                              2-methyl-6-                                                                              7.28-7.91(m, 5H);                                                  chlorophenyl                                                                             3.94(s, 3H); 3.76(s, 3H);                                                     2.61(s, 3H); 2.39(s, 3H);                                                     2.17(s, 3H).                                  3.23  CH.sub.3                                                                             CH.sub.3                                                                              4-methylphenyl                                                                           7.23-8.11(m, 6H);                                                             3.91(s, 3H); 3.75(s, 3H);                                                     2.61(s, 3H); 2.39(s, 3H);                                                     2.36(s, 3H).                                  3.24  CH.sub.3                                                                             CH.sub.3                                                                              2-ethylphenyl                                                                            6.98-7.63(m, 6H);                                                             3.89(s, 3H); 3.74(s, 3H);                                                     2.71(s, 3H); 2.48(s, 3H);                                                     2.37(s, 3H); 1.12(t, 3H).                     3.25  CH.sub.3                                                                             CH.sub.3                                                                              2-fluorophenyl                                                                           7.20-8.27(m, 6H);                                                             3.93(s, 3H); 3.74(s, 3H);                                                     2.61(s, 3H); 2.38(s, 3H).                     3.26  CH.sub.3                                                                             CH.sub.3                                                                              2-biphenylyl                                                                             7.17-7.64(m, 11H);                                                            3.83(s, 3H); 3.62(s, 3H);                                                     2.47(s, 3H); 2.30(s, 3H).                     3.27  CH.sub.3                                                                             CH.sub.3                                                                              3,4-dichlorophenyl                                                                       7.55-8.32(m, 5H);                                                             3.91(s, 3H); 3.73(s, 3H);                                                     2.62(s, 3H); 2.37(s, 3H).                     3.28  CH.sub.3                                                                             CH.sub.3                                                                              3,5-dichlorophenyl                                                                       7.23-8.18(m, 5H);                                                             3.91(s, 3H); 3.73(s, 4H);                                                     2.63(s, 3H); 2.38(s, 3H)                      3.29  CH.sub.3                                                                             CH.sub.3                                                                              4-methyl-3-chloro-                                                                       7.19-8.08(m, 5H);                                                  phenyl     3.87(s, 3H); 3.72                                                             (s, 3H); 2.63(s, 3H);                                                         2.36(s, 3H); 2.30(s, 3H).                     3.30  CH.sub.3                                                                             CH.sub.3                                                                              3-cyanophenyl                                                                            7.58-8.22(m, 6H);                                                             3.91(s, 3H); 3.75(s, 3H);                                                     2.63(s, 3H); 2.39(s, 3H).                     3.31  CH.sub.3                                                                             CH.sub.3                                                                              3-chlorophenyl                                                                           7.25-8.17(m, 6H);                                                             3.92(s, 3H); 3.74(s, 3H);                                                     2.61(s, 3H); 2.39(s, 3H).                     3.32  CH.sub.3                                                                             CH.sub.3                                                                              3-fluorophenyl                                                                           6.96-8.18(m, 6H);                                                             3.91(s, 3H); 3.74(s, 3H);                                                     2.62(s, 3H); 2.39(s, 3H).                     3.33  CH.sub.3                                                                             CH.sub.3                                                                              3-methoxyphenyl                                                                          6.82-8.17(m, 6H);                                                             3.92(s, 3H); 3.89(s, 3H);                                                     3.75(s, 3H); 2.60(s, 3H);                                                     2.38(s, 3H).                                  3.34  CH.sub.3                                                                             OCH.sub.3                                                                             2-methylphenyl                                                                           6.98-7.60(m, 6H);                                                             3.96(s, 3H); 3.87(s, 3H);                                                     3.70(s, 3H); 2.61(s, 3H);                                                     2.18(s, 3H).                                  3.35  CH.sub.3                                                                             OCH.sub.3                                                                             2,5-dichlorophenyl                                                                       7.24-8.19(m, 5H);                                                             3.98(s, 3H); 3.87(s, 3H);                                                     3.73(s, 3H); 2.54(s, 3H).                     3.36  CH.sub.3                                                                             CH.sub.3                                                                              2,4,5-trichloro-                                                                         7.63-8.24(m, 4H);                                                  phenyl     3.91(s, 3H); 3.75(s, 3H);                                                     2.61(s, 3H); 2.37(s, 3H).                     3.37  CH.sub.3                                                                             CH.sub.3                                                                              3-ethylphenyl                                                                            7.11-8.16(m, 6H);                                                             3.90(s, 3H); 3.74(s, 3H);                                                     2.72(t, 2H); 2.62(s, 3H);                                                     2.37(s, 3H); 1.28(t, 4H).                     3.38  CH.sub.3                                                                             CH.sub.3                                                                              2-benzylphenyl                                                                           7.29-7.96(m, 11H);                                                            4.02(s, 2H); 3.94(s, 3H);                                                     3.76(s, 3H); 2.59(s, 3H);                                                     2.38(s, 3H).                                  3.39  CH.sub.3                                                                             CH.sub.3                                                                              2-phenoxyphenyl                                                                          7.00-8.38(m, 11H);                                                            3.85(s, 3H); 3.68(s, 3H);                                                     2.49(s, 3H); 2.34(s, 3H).                     3.40  CH.sub.3                                                                             CH.sub.3                                                                              3,5-dimethylphenyl                                                                       6.92-8.11(m, 5H);                                                             3.91(s, 3H); 3.76(s, 3H);                                                     2.62(s, 3H); 2.40(s, 6H);                                                     2.38(s, 3H).                                  3.41  CH.sub.3                                                                             CH.sub.3                                                                              1-naphthyl 7.52-8.11(m, 9H);                                                             3.93(s, 3H); 3.77(s, 3H);                                                     2.62(s, 3H); 2.39(s, 3H).                     ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                         ##STR45##                                                                    Comp.                                                                         No.    R.sub.1 R.sub.2  R.sub.4      physical data                            ______________________________________                                        4.01   CH.sub.3                                                                              CH.sub.3 2,3-dichlorophenyl                                    4.02   CH.sub.3                                                                              CH.sub.3 2-chlorophenyl                                        4.03   CH.sub.3                                                                              CH.sub.3 2,4-dichlorophenyl                                    4.04   CH.sub.3                                                                              CH.sub.3 2,5-dichlorophenyl                                    4.05   CH.sub.3                                                                              CH.sub.3 2,6-dichlorophenyl                                    4.06   CH.sub.3                                                                              CH.sub.3 2-methylphenyl                                        4.07   CH.sub.3                                                                              CH.sub.3 2-isopropylphenyl                                     4.08   CH.sub.3                                                                              CH.sub.3 2-CF.sub.3 -phenyl                                    4.09   CH.sub.3                                                                              CH.sub.3 2-methoxyphenyl                                       4.10   CH.sub.3                                                                              CH.sub.3 2-methyl-5-                                                                   chlorophenyl                                          4.11   CH.sub.3                                                                              CH.sub.3 phenyl                                                4.12   CH.sub.3                                                                              CH.sub.3 3-methylphenyl                                        4.13   CH.sub.3                                                                              CH.sub.3 2-chloro-4-                                                                   methylphenyl                                          4.14   CH.sub.3                                                                              CH.sub.3 2-cyano-4-                                                                    chlorophenyl                                          4.15   CH.sub.3                                                                              CH.sub.3 3-CF.sub.3 -phenyl                                    4.16   CH.sub.3                                                                              CH.sub.3 4-chlorophenyl                                        4.17   CH.sub.3                                                                              CH.sub.3 2-cyanophenyl                                         4.18   CH.sub.3                                                                              CH.sub.3 2-methyl-3-                                                                   chlorophenyl                                          4.19   CH.sub.3                                                                              CH.sub.3 2-methyl-4-                                                                   chlorophenyl                                          4.20   CH.sub.3                                                                              CH.sub.3 2,3-dimethylphenyl                                    4.21   CH.sub.3                                                                              CH.sub.3 2,6-dimethylphenyl                                    4.22   CH.sub.3                                                                              CH.sub.3 2-methyl-6-                                                                   chlorophenyl                                          4.23   CH.sub.3                                                                              CH.sub.3 4-methylphenyl                                        4.24   CH.sub.3                                                                              CH.sub.3 2-ethylphenyl                                         4.25   CH.sub.3                                                                              CH.sub.3 2-fluorophenyl                                        4.26   CH.sub.3                                                                              CH.sub.3 2-biphenylyl                                          4.27   CH.sub.3                                                                              CH.sub.3 3,4-dichlorophenyl                                    4.28   CH.sub.3                                                                              CH.sub.3 3,5-dichlorophenyl                                    4.29   CH.sub.3                                                                              CH.sub.3 4-methyl-3-chloro-                                                            phenyl                                                4.30   CH.sub.3                                                                              CH.sub.3 3-cyanophenyl                                         4.31   CH.sub.3                                                                              CH.sub.3 3-chlorophenyl                                        4.32   CH.sub.3                                                                              CH.sub.3 3-fluorophenyl                                        4.33   CH.sub.3                                                                              CH.sub.3 3-methoxyphenyl                                       4.34   CH.sub.3                                                                              OCH.sub.3                                                                              2-methylphenyl                                        4.35   CH.sub.3                                                                              OCH.sub.3                                                                              2,5-dichlorophenyl                                    4.36   CH.sub.3                                                                              CH.sub.3 2,4,5-trichlorophenyl                                 ______________________________________                                    

                                      TABLE 5                                     __________________________________________________________________________     ##STR46##                                                                    Comp.                                                                         No.  R.sub.1                                                                            R.sub.2                                                                            R.sub.3                                                                          R.sub.4     physical data                                   __________________________________________________________________________    5.01 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2,3-dichlorophenyl                                          5.02 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-chlorophenyl                                              5.03 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2,4-dichlorophenyl                                          5.04 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2,5-dichlorophenyl                                          5.05 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2,6-dichlorophenyl                                          5.06 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2,4,5-trichlorophenyl                                       5.07 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2,4,6-trichlorophenyl                                       5.08 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-CF.sub.3 -phenyl                                          5.09 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-fluorophenyl                                              5.10 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-methyl-5-                                                                   chlorophenyl                                                5.11 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         phenyl                                                      5.12 CH.sub.3                                                                           CH.sub.3                                                                           H  phenyl                                                      5.13 CH.sub.3                                                                           CH.sub.3                                                                           H  2-chlorophenyl                                              5.14 CH.sub.3                                                                           CH.sub.3                                                                           H  2,4-dichlorophenyl                                          5.15 CH.sub.3                                                                           CH.sub.3                                                                           H  2-fluorophenyl                                              5.16 CH.sub.3                                                                           CH.sub.3                                                                           H  benzyl                                                      5.17 CH.sub.3                                                                           CH.sub.3                                                                           H  2,6-dichlorobenzyl                                          5.18 CH.sub.3                                                                           CH.sub.3                                                                           H                                                                                 ##STR47##                                                  5.19 CH.sub.3                                                                           CH.sub.3                                                                           H  3-methoxybenzyl                                             5.20 CH.sub.3                                                                           CH.sub.3                                                                           H  4-methoxybenzyl                                             5.21 CH.sub.3                                                                           N(CH.sub.3).sub.2                                                                  H  phenyl                                                      5.22 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-cyanophenyl                                               5.23 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-chlorophenyl                                              5.24 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-CF.sub.3 -phenyl                                          5.25 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-nitrophenyl                                               5.26 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-methoxy-5-chloro-                                                           phenyl                                                      5.27 CH.sub.3                                                                           CH.sub.3                                                                           H  2-methylphenyl                                              5.28 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3,4-dichlorophenyl                                          5.29 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-nitrophenyl                                               5.30 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-CF.sub.3 -4-chloro-                                                         phenyl                                                      5.31 CH.sub.3                                                                           OCH.sub.3                                                                          H  2-chlorophenyl                                              5.32 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         2-chlorophenyl                                              5.33 CH.sub.3                                                                           OCH.sub.3                                                                          H  2-methoxybenzyl                                             5.34 C.sub.2 H.sub.5                                                                    OCH.sub.3                                                                          H  2-methoxybenzyl                                             5.35 CH.sub.3                                                                           OCH.sub.3                                                                          H  2-chlorobenzyl                                              5.36 C.sub.2 H.sub.5                                                                    OCH.sub.3                                                                          H  2-chlorobenzyl                                              5.37 CH.sub.3                                                                           CH.sub.3                                                                           H  2-methoxybenzyl                                             5.38 CH.sub.3                                                                           CH.sub.3                                                                           H  2,5-dichlorophenyl                                          5.39 CH.sub.3                                                                           CH.sub.3                                                                           H                                                                                 ##STR48##                                                  5.40 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-methoxyphenyl                                             5.41 CH.sub.3                                                                           CH.sub.3                                                                           H  3-chlorophenyl                                              5.42 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3,5-dichlorophenyl                                          5.43 CH.sub.3                                                                           SCH.sub.3                                                                          H                                                                                 ##STR49##                                                  5.44 CH.sub.3                                                                           OCH.sub.3                                                                          H  3-chlorophenyl                                              5.45 CH.sub.3                                                                           OCH.sub.3                                                                          H                                                                                 ##STR50##                                                  5.46 CH.sub.3                                                                           CH.sub.3                                                                           H  3-cyanophenyl                                               5.47 CH.sub.3                                                                           CH.sub.3                                                                           H  4-biphenylyl                                                5.48 CH.sub.3                                                                           CH.sub.3                                                                           H                                                                                 ##STR51##                                                  5.49 CH.sub.3                                                                           CH.sub.3                                                                           H                                                                                 ##STR52##                                                  5.50 CH.sub.3                                                                           CH.sub.3                                                                           H  3,4-dichlorophenyl                                          5.51 CH.sub.3                                                                           CH.sub.3                                                                           H  3-CF.sub.3 -phenyl                                          5.52 CH.sub.3                                                                           CH.sub.3                                                                           H  3-methoxyphenyl                                             5.53 CH.sub.3                                                                           CH.sub.3                                                                           H                                                                                 ##STR53##                                                  5.54 CH.sub.3                                                                           CH.sub.3                                                                           H  2-nitrophenyl                                               5.55 CH.sub.3                                                                           CH.sub.3                                                                           H  3-nitrophenyl                                               5.56 CH.sub.3                                                                           CH.sub.3                                                                           H  2,6-dichlorophenyl                                          5.57 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         5-CF.sub.3 -2-chloro-                                                         phenyl                                                      5.58 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         4-biphenylyl                                                5.59 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                          ##STR54##                                                  5.60 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                          ##STR55##                                                  5.61 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3,4-dimethoxyphenyl                                         5.62 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-pyridyl                                                   5.63 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         4-phenoxyphenyl                                             5.64 CH.sub.3                                                                           CH.sub.3                                                                           H  2-methyl-5-chloro-                                                            phenyl                                                      5.65 CH.sub.3                                                                           CH.sub.3                                                                           H  4-chlorophenyl                                              5.66 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-fluorophenyl                                              5.67 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                          ##STR56##                                                  5.68 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         4-fluorophenyl                                              5.69 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         4-chlorophenyl                                              5.70 CH.sub.3                                                                           OCH.sub.3                                                                          H  3,4-dichlorophenyl                                          5.71 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         3-CF.sub.3 -phenyl                                          5.72 N(CH.sub.3).sub.2                                                                  CH.sub.3                                                                           H  3-chlorophenyl                                              5.73 CH.sub.3                                                                           CH.sub.3                                                                           H  3-CF.sub.3 -phenyl                                          5.74 CH.sub.3                                                                           OCH.sub.3                                                                          H  2,5-dichlorophenyl                                          5.75 H    CH.sub.3                                                                           H  3-CF.sub.3 -phenyl                                          5.76 CH.sub.3                                                                           OCH.sub.3                                                                          H  5-chloro-2-                                                                   methylphenyl                                                5.77 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-chloro-2-                                                                   methylphenyl                                                5.78 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         4-chloro-2-                                                                   methylphenyl                                                5.79 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         3-chlorophenyl                                              5.80 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         4-chlorophenyl                                              5.81 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         3,4-dichlorophenyl                                          5.82 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         2,3-dichlorophenyl                                          5.83 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         3,5-dichlorophenyl                                          5.84 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         4-chloro-2-                                                                   methylphenyl                                                5.85 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         3-chloro-2-                                                                   methylphenyl                                                5.86 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         2,4-dichlorophenyl                                          5.87 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         5-chloro-2-                                                                   methylphenyl                                                5.88 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-bromophenyl                                               5.89 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         4-bromophenyl                                               5.90 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         3-bromophenyl                                               5.91 CH.sub.3                                                                           OCH.sub.3                                                                          H  3-bromophenyl                                               5.92 CH.sub.3                                                                           OCH.sub.3                                                                          H  4-methylphenyl                                              5.93 CH.sub.3                                                                           CH.sub.3                                                                           H  4-bromophenyl                                               5.94 CH.sub.3                                                                           CH.sub.3                                                                           H  4-bromophenyl                                               5.95 CH.sub.3                                                                           CH.sub.3                                                                           H  3-bromophenyl                                               5.96 CH.sub.3                                                                           CH.sub.3                                                                           H  4-bromophenyl                                               5.97 CH.sub.3                                                                           CH.sub.3                                                                           H  4-methylphenyl                                              5.98 CH.sub.3                                                                           CH.sub.3                                                                           H  2,5-dimethylphenyl                                          5.99 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3,5-dimethylphenyl                                          __________________________________________________________________________

                  TABLE 6                                                         ______________________________________                                         ##STR57##                                                                    Comp.                                                                         No.   R.sub.1                                                                              R.sub.2  R.sub.3                                                                            R.sub.4     physical data                          ______________________________________                                        6.01  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           2,3-dichlorophenyl                                 6.02  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           2-chlorophenyl                                     6.03  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           2,4-dichlorophenyl                                 6.04  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           2,5-dichlorophenyl                                 6.05  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           2,6-dichlorophenyl                                 6.06  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           2,4,5-trichlorophenyl                              6.07  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           2,4,6-trichlorophenyl                              6.08  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           2-CF.sub.3 -phenyl                                 6.09  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           2-fluorophenyl                                     6.10  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           2-methyl-5-                                                                   chlorophenyl                                       6.11  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           phenyl                                             6.12  CH.sub.3                                                                             CH.sub.3 H    phenyl                                             6.13  CH.sub.3                                                                             CH.sub.3 H    2-chlorophenyl                                     6.14  CH.sub.3                                                                             CH.sub.3 H    2,4-dichlorophenyl                                 6.15  CH.sub.3                                                                             CH.sub.3 H    2-fluorophenyl                                     6.16  CH.sub.3                                                                             CH.sub.3 H    benzyl                                             6.17  CH.sub.3                                                                             CH.sub.3 H    2,6-dichlorobenzyl                                 6.18  CH.sub.3                                                                             CH.sub.3 H                                                                                   ##STR58##                                         6.19  CH.sub.3                                                                             CH.sub.3 H    3-methoxybenzyl                                    6.20  CH.sub.3                                                                             CH.sub.3 H    4-methoxybenzyl                                    6.21  CH.sub.3                                                                             N(CH.sub.3).sub.2                                                                      H    phenyl                                             6.22  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           2-cyanophenyl                                      6.23  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           3-chlorophenyl                                     6.24  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           3-CF.sub.3 -phenyl                                 6.25  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           2-nitrophenyl                                      6.26  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           2-methoxy-5-chloro-                                                           phenyl                                             6.27  CH.sub.3                                                                             CH.sub.3 H    2-methylphenyl                                     6.28  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           3,4-dichlorophenyl                                 6.29  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           3-nitrophenyl                                      6.30  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           3-CF.sub.3 -4-chloro-                                                         phenyl                                             6.31  CH.sub.3                                                                             OCH.sub.3                                                                              H    2-chlorophenyl                                     6.32  CH.sub.3                                                                             OCH.sub.3                                                                              CH.sub.3                                                                           2-chlorophenyl                                     6.33  CH.sub.3                                                                             OCH.sub.3                                                                              H    2-methoxybenzyl                                    6.34  C.sub.2 H.sub.5                                                                      OCH.sub.3                                                                              H    2-methoxybenzyl                                    6.35  CH.sub.3                                                                             OCH.sub.3                                                                              H    2-chlorobenzyl                                     6.36  C.sub.2 H.sub.5                                                                      OCH.sub.3                                                                              H    2-chlorobenzyl                                     6.37  CH.sub.3                                                                             CH.sub.3 H    2-methoxybenzyl                                    6.38  CH.sub.3                                                                             CH.sub.3 H    2,5-dichlorophenyl                                 6.39  CH.sub.3                                                                             CH.sub.3 H                                                                                   ##STR59##                                         6.40  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           3-methoxyphenyl                                    6.41  CH.sub.3                                                                             CH.sub.3 H    3-chlorophenyl                                     6.42  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           3,5-dichlorophenyl                                 6.43  CH.sub.3                                                                             SCH.sub.3                                                                              H                                                                                   ##STR60##                                         6.44  CH.sub.3                                                                             OCH.sub.3                                                                              H    3-chlorophenyl                                     6.45  CH.sub.3                                                                             OCH.sub.3                                                                              H                                                                                   ##STR61##                                         6.46  CH.sub.3                                                                             CH.sub.3 H    3-cyanophenyl                                      6.47  CH.sub.3                                                                             CH.sub.3 H    4-biphenylyl                                       6.48  CH.sub.3                                                                             CH.sub.3 H                                                                                   ##STR62##                                         6.49  CH.sub.3                                                                             CH.sub.3 H                                                                                   ##STR63##                                         6.50  CH.sub.3                                                                             CH.sub.3 H    3,4-dichlorophenyl                                 6.51  CH.sub.3                                                                             CH.sub.3 H    3-CF.sub.3 -phenyl                                 6.52  CH.sub.3                                                                             CH.sub.3 H    3-methoxyphenyl                                    6.53  CH.sub.3                                                                             CH.sub.3 H                                                                                   ##STR64##                                         6.54  CH.sub.3                                                                             CH.sub.3 H    2-nitrophenyl                                      6.55  CH.sub.3                                                                             CH.sub.3 H    3-nitrophenyl                                      6.56  CH.sub.3                                                                             CH.sub.3 H    2,6-dichlorophenyl                                 6.57  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           5-CF.sub.3 -2-chloro-                                                         phenyl                                             6.58  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           4-biphenylyl                                       6.59  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                            ##STR65##                                         6.60  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                            ##STR66##                                         6.61  CH.sub.3                                                                             CH.sub.3 CH.sub.3                                                                           3,4-dimethoxyphenyl                                ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                         ##STR67##                                                                    Comp.                                                                         No.    R.sub.1 R.sub.2  R.sub.4      physical data                            ______________________________________                                        7.01   CH.sub.3                                                                              CH.sub.3 2,3-dichlorophenyl                                    7.02   CH.sub.3                                                                              CH.sub.3 2-chlorophenyl                                        7.03   CH.sub.3                                                                              CH.sub.3 2,4-dichlorophenyl                                    7.04   CH.sub.3                                                                              CH.sub.3 2,5-dichlorophenyl                                    7.05   CH.sub.3                                                                              CH.sub.3 2,6-dichlorophenyl                                    7.06   CH.sub.3                                                                              CH.sub.3 2-methylphenyl                                        7.07   CH.sub.3                                                                              CH.sub.3 2-isopropylphenyl                                     7.08   CH.sub.3                                                                              CH.sub.3 2-CF.sub.3 -phenyl                                    7.09   CH.sub.3                                                                              CH.sub.3 2-methoxyphenyl                                       7.10   CH.sub.3                                                                              CH.sub.3 2-methyl-5-                                                                   chlorophenyl                                          7.11   CH.sub.3                                                                              CH.sub.3 phenyl                                                7.12   CH.sub.3                                                                              CH.sub.3 3-methylphenyl                                        7.13   CH.sub.3                                                                              CH.sub.3 2-chloro-4-                                                                   methylphenyl                                          7.14   CH.sub.3                                                                              CH.sub.3 2-cyano-4-                                                                    chlorophenyl                                          7.15   CH.sub.3                                                                              CH.sub.3 3-CF.sub.3 -phenyl                                    7.16   CH.sub.3                                                                              CH.sub.3 4-chlorophenyl                                        7.17   CH.sub.3                                                                              CH.sub.3 2-cyanophenyl                                         7.18   CH.sub.3                                                                              CH.sub.3 2-methyl-3-                                                                   chlorophenyl                                          7.19   CH.sub.3                                                                              CH.sub.3 2-methyl-4-                                                                   chlorophenyl                                          7.20   CH.sub.3                                                                              CH.sub.3 2,3-dimethylphenyl                                    7.21   CH.sub.3                                                                              CH.sub.3 2,6-dimethylphenyl                                    7.22   CH.sub.3                                                                              CH.sub.3 2-methyl-6-                                                                   chlorophenyl                                          7.23   CH.sub.3                                                                              CH.sub.3 4-methylphenyl                                        7.24   CH.sub.3                                                                              CH.sub.3 2-ethylphenyl                                         7.25   CH.sub.3                                                                              CH.sub.3 2-fluorophenyl                                        7.26   CH.sub.3                                                                              CH.sub.3 2-biphenylyl                                          7.27   CH.sub.3                                                                              CH.sub.3 3,4-dichlorophenyl                                    7.28   CH.sub.3                                                                              CH.sub.3 3,5-dichlorophenyl                                    7.29   CH.sub.3                                                                              CH.sub.3 4-methyl-3-chloro-                                                            phenyl                                                7.30   CH.sub.3                                                                              CH.sub.3 3-cyanophenyl                                         7.31   CH.sub.3                                                                              CH.sub.3 3-chlorophenyl                                        7.32   CH.sub.3                                                                              CH.sub.3 3-fluorophenyl                                        7.33   CH.sub.3                                                                              CH.sub.3 3-methoxyphenyl                                       7.34   CH.sub.3                                                                              OCH.sub.3                                                                              2-methylphenyl                                        7.35   CH.sub.3                                                                              OCH.sub.3                                                                              2,5-dichlorophenyl                                    7.36   CH.sub.3                                                                              CH.sub.3 2,4,5-trichlorophenyl                                 ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                         ##STR68##                                                                    Comp.                                                                         No.    R.sub.1 R.sub.2  R.sub.4      physical data                            ______________________________________                                        8.01   CH.sub.3                                                                              CH.sub.3 2,3-dichlorophenyl                                    8.02   CH.sub.3                                                                              CH.sub.3 2-chlorophenyl                                        8.03   CH.sub.3                                                                              CH.sub.3 2,4-dichlorophenyl                                    8.04   CH.sub.3                                                                              CH.sub.3 2,5-dichlorophenyl                                    8.05   CH.sub.3                                                                              CH.sub.3 2,6-dichlorophenyl                                    8.06   CH.sub.3                                                                              CH.sub.3 2-methylphenyl                                        8.07   CH.sub.3                                                                              CH.sub.3 2-isopropylphenyl                                     8.08   CH.sub.3                                                                              CH.sub.3 2-CF.sub.3 -phenyl                                    8.09   CH.sub.3                                                                              CH.sub.3 2-methoxyphenyl                                       8.10   CH.sub.3                                                                              CH.sub.3 2-methyl-5-                                                                   chlorophenyl                                          8.11   CH.sub.3                                                                              CH.sub.3 phenyl                                                8.12   CH.sub.3                                                                              CH.sub.3 3-methylphenyl                                        8.13   CH.sub.3                                                                              CH.sub.3 2-chloro-4-                                                                   methylphenyl                                          8.14   CH.sub.3                                                                              CH.sub.3 2-cyano-4-                                                                    chlorophenyl                                          8.15   CH.sub.3                                                                              CH.sub.3 3-CF.sub.3 -phenyl                                    8.16   CH.sub.3                                                                              CH.sub.3 4-chlorophenyl                                        8.17   CH.sub.3                                                                              CH.sub.3 2-cyanophenyl                                         8.18   CH.sub.3                                                                              CH.sub.3 2-methyl-3-                                                                   chlorophenyl                                          8.19   CH.sub.3                                                                              CH.sub.3 2-methyl-4-                                                                   chlorophenyl                                          8.20   CH.sub.3                                                                              CH.sub.3 2,3-dimethylphenyl                                    8.21   CH.sub.3                                                                              CH.sub.3 2,6-dimethylphenyl                                    8.22   CH.sub.3                                                                              CH.sub.3 2-methyl-6-                                                                   chlorophenyl                                          8.23   CH.sub.3                                                                              CH.sub.3 4-methylphenyl                                        8.24   CH.sub.3                                                                              CH.sub.3 2-ethylphenyl                                         8.25   CH.sub.3                                                                              CH.sub.3 2-fluorophenyl                                        8.26   CH.sub.3                                                                              CH.sub.3 2-biphenylyl                                          8.27   CH.sub.3                                                                              CH.sub.3 3,4-dichlorophenyl                                    8.28   CH.sub.3                                                                              CH.sub.3 3,5-dichlorophenyl                                    8.29   CH.sub.3                                                                              CH.sub.3 4-methyl-3-chloro-                                                            phenyl                                                8.30   CH.sub.3                                                                              CH.sub.3 3-cyanophenyl                                         8.31   CH.sub.3                                                                              CH.sub.3 3-chlorophenyl                                        8.32   CH.sub.3                                                                              CH.sub.3 3-fluorophenyl                                        8.33   CH.sub.3                                                                              CH.sub.3 3-methoxyphenyl                                       8.34   CH.sub.3                                                                              OCH.sub.3                                                                              2-methylphenyl                                        8.35   CH.sub.3                                                                              OCH.sub.3                                                                              2,5-dichlorophenyl                                    8.36   CH.sub.3                                                                              CH.sub.3 2,4,5-trichlorophenyl                                 ______________________________________                                    

                                      TABLE 9                                     __________________________________________________________________________     ##STR69##                                                                    Comp.                                                                         No.  R.sub.1                                                                            R.sub.2                                                                            R.sub.3                                                                          R.sub.4     physical data                                   __________________________________________________________________________    9.01 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2,3-dichlorophenyl                                          9.02 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-chlorophenyl                                              9.03 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2,4-dichlorophenyl                                          9.04 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2,5-dichlorophenyl                                          9.05 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2,6-dichlorophenyl                                          9.06 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2,4,5-                                                                        trichlorophenyl                                             9.07 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2,4,6-                                                                        trichlorophenyl                                             9.08 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-CF.sub.3 -phenyl                                          9.09 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-fluorophenyl                                              9.10 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-methyl-5-                                                                   chlorophenyl                                                9.11 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         phenyl                                                      9.12 CH.sub.3                                                                           CH.sub.3                                                                           H  phenyl                                                      9.13 CH.sub.3                                                                           CH.sub.3                                                                           H  2-chlorophenyl                                              9.14 CH.sub.3                                                                           CH.sub.3                                                                           H  2,4-dichlorophenyl                                          9.15 CH.sub.3                                                                           CH.sub.3                                                                           H  2-fluorophenyl                                              9.16 CH.sub.3                                                                           CH.sub.3                                                                           H  benzyl                                                      9.17 CH.sub.3                                                                           CH.sub.3                                                                           H  2,6-dichlorobenzyl                                          9.18 CH.sub.3                                                                           CH.sub.3                                                                           H                                                                                 ##STR70##                                                  9.19 CH.sub.3                                                                           CH.sub.3                                                                           H  3-methoxybenzyl                                             9.20 CH.sub.3                                                                           CH.sub.3                                                                           H  4-methoxybenzyl                                             9.21 CH.sub.3                                                                           N(CH.sub.3).sub.2                                                                  H  phenyl                                                      9.22 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-cyanophenyl                                               9.23 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-chlorophenyl                                              9.24 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-CF.sub.3 -phenyl                                          9.25 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-nitrophenyl                                               9.26 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-methoxy-5-                                                                  chloro-phenyl                                               9.27 CH.sub.3                                                                           CH.sub.3                                                                           H  2-methylphenyl                                              9.28 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3,4-dichlorophenyl                                          9.29 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-nitrophenyl                                               9.30 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-CF.sub.3 -4-chloro-                                                         phenyl                                                      9.31 CH.sub.3                                                                           OCH.sub.3                                                                          H  2-chlorophenyl                                              9.32 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         2-chlorophenyl                                              9.33 CH.sub.3                                                                           OCH.sub.3                                                                          H  2-methoxybenzyl                                             9.34 C.sub.2 H.sub.5                                                                    OCH.sub.3                                                                          H  2-methoxybenzyl                                             9.35 CH.sub.3                                                                           OCH.sub.3                                                                          H  2-chlorobenzyl                                              9.36 C.sub.2 H.sub.5                                                                    OCH.sub.3                                                                          H  2-chlorobenzyl                                              9.37 CH.sub.3                                                                           CH.sub.3                                                                           H  2-methoxybenzyl                                             9.38 CH.sub.3                                                                           CH.sub.3                                                                           H  2,5-dichlorophenyl                                          9.39 CH.sub.3                                                                           CH.sub.3                                                                           H                                                                                 ##STR71##                                                  9.40 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-methoxyphenyl                                             9.41 CH.sub.3                                                                           CH.sub.3                                                                           H  3-chlorophenyl                                              9.42 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3,5-dichlorophenyl                                          9.43 CH.sub.3                                                                           SCH.sub.3                                                                          H                                                                                 ##STR72##                                                  9.44 CH.sub.3                                                                           OCH.sub.3                                                                          H  3-chlorophenyl                                              9.45 CH.sub.3                                                                           OCH.sub.3                                                                          H                                                                                 ##STR73##                                                  9.46 CH.sub.3                                                                           CH.sub.3                                                                           H  3-cyanophenyl                                               9.47 CH.sub.3                                                                           CH.sub.3                                                                           H  4-biphenylyl                                                9.48 CH.sub.3                                                                           CH.sub.3                                                                           H                                                                                 ##STR74##                                                  9.49 CH.sub.3                                                                           CH.sub.3                                                                           H                                                                                 ##STR75##                                                  9.50 CH.sub.3                                                                           CH.sub.3                                                                           H  3,4-dichlorophenyl                                          9.51 CH.sub.3                                                                           CH.sub.3                                                                           H  3-CF.sub.3 -phenyl                                          9.52 CH.sub.3                                                                           CH.sub.3                                                                           H  3-methoxyphenyl                                             9.53 CH.sub.3                                                                           CH.sub.3                                                                           H                                                                                 ##STR76##                                                  9.54 CH.sub.3                                                                           CH.sub.3                                                                           H  2-nitrophenyl                                               9.55 CH.sub.3                                                                           CH.sub.3                                                                           H  3-nitrophenyl                                               9.56 CH.sub.3                                                                           CH.sub.3                                                                           H  2,6-dichlorophenyl                                          9.57 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         5-CF.sub.3 -2-chloro-                                                         phenyl                                                      9.58 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         4-biphenylyl                                                9.59 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                          ##STR77##                                                  9.60 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                          ##STR78##                                                  9.61 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3,4-                                                                          dimethoxyphenyl                                             9.62 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         2-pyridyl                                                   9.63 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         4-phenoxyphenyl                                             9.64 CH.sub.3                                                                           CH.sub.3                                                                           H  2-methyl-5-chloro-                                                            phenyl                                                      9.65 CH.sub.3                                                                           CH.sub.3                                                                           H  4-chlorophenyl                                              9.66 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-fluorophenyl                                              9.67 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                          ##STR79##                                                  9.68 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         4-fluorophenyl                                              9.69 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         4-chlorophenyl                                              9.70 CH.sub.3                                                                           OCH.sub.3                                                                          H  3,4-dichlorophenyl                                          9.71 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         3-CF.sub.3 -phenyl                                          9.72 N(CH.sub.3).sub.2                                                                  CH.sub.3                                                                           H  3-chlorophenyl                                              9.73 CH.sub.3                                                                           OCH.sub.3                                                                          H  3-CF.sub.3 -phenyl                                          9.74 CH.sub.3                                                                           OCH.sub.3                                                                          H  2,5-dichlorophenyl                                          9.75 H    CH.sub.3                                                                           H  3-CF.sub.3 -phenyl                                          9.76 CH.sub.3                                                                           OCH.sub.3                                                                          H  5-chloro-2-                                                                   methylphenyl                                                9.77 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-chloro-2-                                                                   methylphenyl                                                9.78 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         4-chloro-2-                                                                   methylphenyl                                                9.79 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         3-chlorophenyl                                              9.80 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         4-chlorophenyl                                              9.81 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         3,4-dichlorophenyl                                          9.82 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         2,3-dichlorophenyl                                          9.83 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         3,5-dichlorophenyl                                          9.83 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         2,4-dichlorophenyl                                          9.84 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         4-chloro-2-                                                                   methylphenyl                                                9.85 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         3-chloro-2-                                                                   methylphenyl                                                9.86 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         2,4-dichlorophenyl                                          9.87 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         5-chloro-2-                                                                   methylphenyl                                                9.88 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3-bromophenyl                                               9.89 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         4-bromophenyl                                               9.90 CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3                                                                         3-bromophenyl                                               9.91 CH.sub.3                                                                           OCH.sub.3                                                                          H  3-bromophenyl                                               9.92 CH.sub.3                                                                           OCH.sub.3                                                                          H  4-methylphenyl                                              9.93 CH.sub.3                                                                           CH.sub.3                                                                           H  4-bromophenyl                                               9.94 CH.sub.3                                                                           OCH.sub.3                                                                          H  2,5-dimethylphenyl                                          9.95 CH.sub.3                                                                           CH.sub.3                                                                           H  3-bromophenyl                                               9.96 CH.sub.3                                                                           CH.sub.3                                                                           H  4-bromophenyl                                               9.97 CH.sub.3                                                                           CH.sub.3                                                                           H  4-bromophenyl                                               9.98 CH.sub.3                                                                           CH.sub.3                                                                           H  2,5-dimethylphenyl                                          9.99 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         3,5-dimethylphenyl                                          __________________________________________________________________________

                  TABLE 10                                                        ______________________________________                                         ##STR80##                                                                    Comp.                                                                         No.    R.sub.1  R.sub.2  R.sub.4     physical data                            ______________________________________                                        10.01  CH.sub.3 CH.sub.3 2,3-dichlorophenyl                                   10.02  CH.sub.3 CH.sub.3 2-chlorophenyl                                       10.03  CH.sub.3 CH.sub.3 2,4-dichlorophenyl                                   10.04  CH.sub.3 CH.sub.3 2,5-dichlorophenyl                                   10.05  CH.sub.3 CH.sub.3 2,6-dichlorophenyl                                   10.06  CH.sub.3 CH.sub.3 2,4,5-trichlorophenyl                                10.07  CH.sub.3 CH.sub.3 2,4,6-trichlorophenyl                                10.08  CH.sub.3 CH.sub.3 2-CF.sub.3 -phenyl                                   10.09  CH.sub.3 CH.sub.3 2-fluorophenyl                                       10.10  CH.sub.3 CH.sub.3 2-methyl-5-                                                                   chlorophenyl                                         10.11  CH.sub.3 CH.sub.3 phenyl                                               10.12  CH.sub.3 N(CH.sub.3).sub.2                                                                      phenyl                                               10.13  CH.sub.3 CH.sub.3 2-cyanophenyl                                        10.14  CH.sub.3 CH.sub.3 2-chlorophenyl                                       10.15  CH.sub.3 CH.sub.3 3-CF.sub.3 -phenyl                                   10.16  CH.sub.3 CH.sub.3 2-nitrophenyl                                        10.17  CH.sub.3 CH.sub.3 2-methoxy-5-chloro-                                                           phenyl                                               10.18  CH.sub.3 CH.sub.3 2-methylphenyl                                       10.19  CH.sub.3 CH.sub.3 3,4-dichlorophenyl                                   10.20  CH.sub.3 CH.sub.3 3-nitrophenyl                                        10.21  CH.sub.3 CH.sub.3 3-CF.sub.3 -chloro-                                                           phenyl                                               10.22  OCH.sub.3                                                                              CH.sub.3 2-chlorophenyl                                       ______________________________________                                    

                  TABLE 11                                                        ______________________________________                                         ##STR81##                                                                    Comp.                                                                         No.    R.sub.1  R.sub.3  R.sub.4     physical data                            ______________________________________                                        11.01  CH.sub.3 CH.sub.3 phenyl                                               11.02  CH.sub.3 H        phenyl                                               11.03  CH.sub.3 H        2-chlorophenyl                                       11.04  CH.sub.3 CH.sub.3 2-chlorophenyl                                       11.05  CH.sub.3 H        2-methoxybenzyl                                      11.06  C.sub.2 H.sub.5                                                                        H        2-methoxybenzyl                                      11.07  C.sub.2 H.sub.5                                                                        H        2-chlorobenzyl                                       11.08  CH.sub.3 H        2-chlorobenzyl                                       11.09  CH.sub.3 H                                                                                       ##STR82##                                           ______________________________________                                    

                  TABLE 12                                                        ______________________________________                                         ##STR83##                                                                    Comp.                                                                         No.      R.sub.1  R.sub.4        physical data                                ______________________________________                                        12.01    CH.sub.3 phenyl                                                      12.02    CH.sub.3 2-methylphenyl                                              12.03    CH.sub.3 2,5-dichlorophenyl                                          ______________________________________                                    

EXAMPLE A Activity Against Powdery Mildew

Sphaeorotheca fuliginea

Plants of Cucumis sativus (cucumber), 7 days old (cotyledon stage), aresprayed to near run off with a suspension containing 63 mg/l of activeingredient. The deposit is then allowed to dry. One day later, thetreated plants are inoculated with a spore suspension containing 1×10⁵/ml of freshly collected conidia of Sphaeorotheca₋₋ fuliginea and thenincubated in the green house for 7 days at +24° C. and 60% r.h.

The efficacy of the test compounds is determined by comparing the degreeof fungal attack with that on untreated similarly inoculated checkplants. In this test compounds 1.03, 1.06, 1.09, 1.10, 1.12, 1.13, 1.38,1.39, 1.40, 1.41, 1.43, 1.44, 1.45, 1.48, 1.51, 1.64, 1.65, 1.66, 1.67,1.68, 1.69, 1.70, 1.71, 1.73, 1.74, 1.75, 1.76, 1.78, 1.79, 1.80, 1.81,1.83, 1.86, 1.88, 1.89, 190, 1.92, 1.93, 1.94, 1.95, 1.96, 1.97, 1.98,3.01, 3.02, 3.03, 3.04, 3.07, 3.08, 3.15, 3.16, 3.31, 3.35, 3.36, 3.37,3.39, 3.40, 3.41 showed an efficacy of more than 90%.

Similar methods are used to test the compounds against the followingpathogens:

Podosphaera luecotricha on apple,

Erysiphe graminis on wheat and barley (dry inoculation),

Uncinula necator on grape.

EXAMPLE B Activity Against Rust, Scab, Pyrenophora, Leptosphaeria

Uromyces appendiculatus

Plants of Phaseolus vulgaris (pole bean), 14 days old (2 leaves stage),are sprayed to near run off with a suspension containing 63 mg/l of theactive ingredient. The deposit is then allowed to dry. One day later,the treated plants are inoculated with a spore suspension containing1×10⁵ /ml of freshly collected spores of Uromyces₋₋ appendiculatus.Incubation is performed for 3 days in a high humidity cabinet at +23° C.and >95% r.h. and thereafter during 10 days at +24° C. and 60% r.h.

The efficacy the compounds is determined by comparing the degree offungal attack with that on untreated, similarly inoculated check plants.In this test compounds 1.01, 1.02, 1.03, 1.04, 1.06, 1.08, 1.09, 1.10,1.11, 1.12, 1.13, 1.17, 1.37, 1.38, 1.39, 1.40, 1.41, 1.43, 1.44, 1.45,1.48, 1.51, 1.64, 1.65, 1.66, 1.67, 1.68, 1.69, 1.70, 1.71, 1.73, 1.74,1.75, 1.76, 1.77, 1.78, 1.79, 1.80, 1.81, 1.83, 1.84, 1.86, 1.88, 1.89,1.90, 1.92, 1.93, 1.94, 1.95, 1.96, 1.97, 1.98, 1.99, 3.01, 3.02, 3.03,3.04, 3.06, 3.07, 3.08, 3.09, 3.15, 3.16, 3.25, 3.31, 3.33, 3.35, 3.37,3.38, 3.39, 3.40 and 3.41 showed an efficacy of at least 90%.

Similar methods are used to test the compounds against the followingpathogens:

Puccinia triticina on wheat (plants 10 days old),

Pyrenophora graminea on barley,

Leptosphaeria nodorum on wheat,

Venturia inaequalis on apple (plants 21 days old; the spore suspensioncontains 1% malt).

EXAMPLE C Activity against Downy Mildew

Plants of Lycopersicon esculentum (tomato) with 6 leaves, are sprayed tonear run off with a spray suspension containing 63 mg/l of the activeingredient. The deposit is then allowed to dry. 1 day later, the treatedplants are inoculated with a spore suspension containing 1×10⁵ /ml offreshly collected sporangia of Phytophthora infestans and then incubatedfor 7 days in a high humidity cabinet at +18° C. and >95% r.h. Theefficacy of the test compounds is determined by comparing the degree offungal attack with that on untreated, similarly inoculated check plants.In this test compounds 1.02, 1.03, 1.04, 1.06, 1.09, 1.10, 1.12, 1.17,1.37, 1.38, 1.40, 1.41, 1.51, 1.65, 1.67, 1.69, 1.71, 1.73, 1.76, 1.78,1.93, 1.95, 1.96, 1.97, 1.98, 3.01, 3.05, 3.06, 3.09, 3.40 and 3.41showed efficacy of at least 90%.

A similar method is used to test the compounds against Plasmoparaviticola on grape vine.

EXAMPLE D Activity After Seed Treatment

The compounds of the invention may also be used for seed treatment. Theadvantageous fungicidal activity is established by in vitro tests withthe following pathogens:

Pyrenophora graminea,

Ustilago nuda,

Gerlachia nivalis,

Leptoshpaeria nodorum,

Autoclaved wheat seeds are inoculated with spores or mycelium of thepathogens and coated with different concentration of the test compoundsresulting in dosages of 50 g a.i./100 kg seed. The treated seeds arethen placed on agar plates and the pathogens allowed to grow for 3-8days at +24° C. in the dark.

The efficacy of the test compounds is determined by comparing the degreeof fungal growth emerging from treated and untreated inoculated seeds.

To evaluate the crop plant tolerance of the compounds, healthy seeds ofwheat and barley are coated with the dosages mentioned above. The seedsare then allowed to germinate in petri dishes on moist filter paper inhigh humidity at +18° C. for 10 days. Plant damage is recorded,comparing the growth of treated and untreated seedlings.

In this test compounds of formula I showed an efficacy of at least 90%against Pyrenophora graminea.

We claim:
 1. A compound of formula I ##STR84## wherein R₁ is hydrogen,C₁₋₄ alkyl, C₁₋₄ alkoxy, C₃₋₆ cycloalkyl, C₁₋₄ alkylthio, or di- C₁₋₄alkylamino,R₂ is hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ alkylthio, ordi- C₁₋₄ alkylamino, R₃ is hydrogen or methyl, R₄ is phenyl, naphthyl,benzyl, phenyethyl, phenylpropyl, 1-phenylethyl, or a heteroarylselected from the group consisting of pyridyl, pyrimidinyl, thienyl,oxazolyl, oxadiazolyl, triazolyl, thiadiazolyl, furyl, isoxazolyl,thiazolyl, imidazolyl, pyridazinyl, quinolinyl, quinazolinyl,benzothienyl, benzofuryl, benzimidazolyl, pyrazolyl, benzothiazolyl,benzoxazolyl, and any one of said heteroaryl groups in combination with--CH₂, --CH₂ --CH₂ -- or --C(CH₃) and wherein each of the aromatic ringsmay be optionally substituted by one, two or three radicles selectedfrom the group consisting of halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄haloalkyl, C₁₋₄ haloalkoxy, C₂₋₈ acyl, benzoyl, C₁₋₄ alkylthio, cyano,phenyl, phenoxy, nitro and --C(CH₃)═N--O--C₁₋₄ alkyl; and X is CH ornitrogen.
 2. A compound according to claim 1 wherein the aromatic ringsin R₄ are optionally substituted by one, two or three radicals selectedfrom the group comprising halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄haloalkyl, C₁₋₄ haloalkoxy, C₁₋₄ alkylthio, cyano, phenyl, phenoxy,nitro, or a group --C(CH₃)═N--O--C₁₋₄ alkyl.
 3. A compound according toclaim 1, wherein R₁ is methyl, ethyl, or cyclopropyl.
 4. A compoundaccording to claim 1, wherein R₂ is methyl, or methoxy.
 5. A compoundaccording to claim 1, wherein the pyrazole ring is linked to the oxygenbridge in the 3- or 4-position.
 6. A compound according to claim 1,wherein R₄ is chlorophenyl, dichlorophenyl, fluorophenyl,methyl-chlorophenyl, trifluoromethylphenyl,trifluoromethyl-chlorophenyl, difluoromethoxyphenyl,trifluoromethoxyphenyl, methylphenyl, or dimethylphenyl.
 7. A compoundaccording to claim 1, wherein R₁ and R₂ are methyl, R₄ is chlorophenyl,dichlorophenyl, fluorophenyl, methyl-chlorophenyl,trifluoromethylphenyl, trifluoromethyl-chlorophenyl,difluoromethoxyphenyl, trifluoromethoxyphenyl, methylphenyl, ordimethylphenyl.
 8. A compound according to claim 7, wherein X is CH. 9.A compound according to claim 1, selected from the groupcomprisingmethyl 2-2,4-dimethyl-6-(1-(3-trifluoromethylphenyl)-1H-pyrazol-3-yloxy)-pyrimidin-5-yl!-3-methoxyacrylate;methyl 2-2,4-dimethyl-6-(1-(3,5-dimethylphenyl)-1H-pyrazol-4-yloxy)-pyrimidin-5-yl!-3-methoxyacrylate;methyl 2-2,4-dimethyl-6-(1-(5-chloro-2-methylphenyl)-1H-pyrazol-3-yloxy)-pyrimidin-5-yl!-3-methoxyacrylate;and methyl 2-2-methyl-4-methoxy-6-(1-(5-chloro-2-methylphenyl)-1H-pyrazol-3-yloxy)-pyrimidin-5-yl!-3-methoxyacrylate.10. Method of combatting phytopathogenic fungi comprising applying tothe fungi or their habitat a fungicidally effective amount of a compoundof formula I according to claim
 1. 11. Fungicidal composition comprisinga compound of formula I stated in claim 1 and a agriculturallyacceptable diluent.
 12. A compound of formula II ##STR85## wherein R₁ ishydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₃₋₆ cycloalkyl, C₁₋₄ alkylthio, ordi- C₁₋₄ alkylamino,R₂ is hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄alkylthio, or di- C₁₋₄ alkylamino, R₃ is hydrogen or methyl, R₄ isphenyl, naphthyl, benzyl, phenyethyl, phenylpropyl, 1-phenylethyl, or aheteroaryl selected from the group consisting of pyridyl, pyrimidinyl,thienyl, oxazolyl, oxadiazolyl, triazolyl, thiadiazolyl, furyl,isoxazolyl, thiazolyl, imidazolyl, pyridazinyl, quinolinyl,quinazolinyl, benzothienyl, benzofuryl, benzimidazolyl, pyrazolyl,benzothiazolyl, benzoxazolyl, and any one of said heteroaryl groups incombination with --CH₂, --CH₂ --CH₂ -- or --C(CH₃) and wherein each ofthe aromatic rings may be optionally substituted by one, two or threeradicles selected from the group consisting of halogen, C₁₋₄ alkyl, C₁₋₄alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, C₂₋₈ acyl, benzoyl, C₁₋₄alkylthio, cyano, phenyl, phenoxy, nitro and --C(CH₃)═N--O--C₁₋₄ alkyl;and X is CH or nitrogen.